Safety remains a persistent challenge for high-energy-density lithium metal batteries(LMBs).The development of safe and non-flammable electrolytes is especially important in harsh conditions such as high temperatures....Safety remains a persistent challenge for high-energy-density lithium metal batteries(LMBs).The development of safe and non-flammable electrolytes is especially important in harsh conditions such as high temperatures.Herein,a flame-retardant,low-cost and thermally stable long chain phosphate ester based(tributyl phosphate,TBP)electrolyte is reported,which can effectively enhance the cycling stability of highly loaded high-nickel LMBs with high safety through co-solvation strategy.The interfacial compatibility between TBP and electrode is effectively improved using a short-chain ether(glycol dimethyl ether,DME),and a specially competitive solvation structure is further constructed using lithium borate difluorooxalate(LiDFOB)to form the stable and inorganic-rich electrode interphases.Benefiting from the presence of the cathode electrolyte interphase(CEI)and solid electrolyte interphase(SEI)enriched with LiF and Li_(x)PO_(y)F_(z),the electrolyte demonstrates excellent cycling stability assembled using a 50μm lithium foil anode in combination with a high loading NMC811(15.4 mg cm^(-2))cathode,with 88%capacity retention after 120 cycles.Furthermore,the electrolyte exhibits excellent high-temperature characteristics when used in a 1-Ah pouch cell(N/P=0.26),and higher thermal runaway temperature(238℃)in the ARC(accelerating rate calorimeter)demonstrating high safety.This novel electrolyte adopts long-chain phosphate as the main solvent for the first time,and would provide a new idea for the development of extremely high safety and high-temperature electrolytes.展开更多
An efficient synthesis of the electrophilic reagent,S-(1,3-dioxoisoindolin-2-yl)O,O-diethyl phosphorothioate(SDDP)is described.Moreover,the synthetic applications of SDDP wherein the transfer of the SP(O)(OEt)_(2) moi...An efficient synthesis of the electrophilic reagent,S-(1,3-dioxoisoindolin-2-yl)O,O-diethyl phosphorothioate(SDDP)is described.Moreover,the synthetic applications of SDDP wherein the transfer of the SP(O)(OEt)_(2) moiety occurs were investigated.In this manner,SDDP underwent facile SP(O)(OEt)_(2) transfer with electron-rich substrates such as ketones,indoles,and thiols to formα-phosphorothiolated ketones,3-phosphorothiolated indoles and S-phosphorothiolated thioethers,respectively.展开更多
基金supported by the National Natural Science Foundation of China (grant No.52072322)the Department of Science and Technology of Sichuan Province (CN) (grant no.23GJHZ0147,23ZDYF0262,2022YFG0294)Research and Innovation Fund for Graduate Students of Southwest Petroleum University (No.:2022KYCX111)。
文摘Safety remains a persistent challenge for high-energy-density lithium metal batteries(LMBs).The development of safe and non-flammable electrolytes is especially important in harsh conditions such as high temperatures.Herein,a flame-retardant,low-cost and thermally stable long chain phosphate ester based(tributyl phosphate,TBP)electrolyte is reported,which can effectively enhance the cycling stability of highly loaded high-nickel LMBs with high safety through co-solvation strategy.The interfacial compatibility between TBP and electrode is effectively improved using a short-chain ether(glycol dimethyl ether,DME),and a specially competitive solvation structure is further constructed using lithium borate difluorooxalate(LiDFOB)to form the stable and inorganic-rich electrode interphases.Benefiting from the presence of the cathode electrolyte interphase(CEI)and solid electrolyte interphase(SEI)enriched with LiF and Li_(x)PO_(y)F_(z),the electrolyte demonstrates excellent cycling stability assembled using a 50μm lithium foil anode in combination with a high loading NMC811(15.4 mg cm^(-2))cathode,with 88%capacity retention after 120 cycles.Furthermore,the electrolyte exhibits excellent high-temperature characteristics when used in a 1-Ah pouch cell(N/P=0.26),and higher thermal runaway temperature(238℃)in the ARC(accelerating rate calorimeter)demonstrating high safety.This novel electrolyte adopts long-chain phosphate as the main solvent for the first time,and would provide a new idea for the development of extremely high safety and high-temperature electrolytes.
基金generous financial support by National Natural Science Foundation of China(No.21472133)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)Key Laboratory of Organic Synthesis of Jiangsu Province(No.KJS1749).
文摘An efficient synthesis of the electrophilic reagent,S-(1,3-dioxoisoindolin-2-yl)O,O-diethyl phosphorothioate(SDDP)is described.Moreover,the synthetic applications of SDDP wherein the transfer of the SP(O)(OEt)_(2) moiety occurs were investigated.In this manner,SDDP underwent facile SP(O)(OEt)_(2) transfer with electron-rich substrates such as ketones,indoles,and thiols to formα-phosphorothiolated ketones,3-phosphorothiolated indoles and S-phosphorothiolated thioethers,respectively.
