Sodium metal anodes(SMAs)sufer from extremely low reversibility(<20%)in carbonate based clectrolytes-this piece of knowledge gained from previous studics has ruled out the application of carbonate solvents for sodi...Sodium metal anodes(SMAs)sufer from extremely low reversibility(<20%)in carbonate based clectrolytes-this piece of knowledge gained from previous studics has ruled out the application of carbonate solvents for sodium metal batteries.Here,we overturn this conclusion by incorporating fluoroethylene carbonate(FEC)as cosolvent that renders a Na plating/stripping fficiency of>95%with conventional NaPF。salt at a regular concentration(1.0M).The peculiar role of FEC is firstly.unraveled via its involvement into the solvation structure,where a threshold FEC concentration with a coordination number>1.2 is needed in guaranteeing high Na reversibility over the long-term.Specifially,by incorporating an average number of 1.2 FEC molecules into the primary Na*solvation sheath,lowest unoccupied molecular orbital(LUMO)levels of such Nat-FEC solvates undergo further decrease,with spin electrons residing either on the O=C 0(O)moiety of FEC or sharing between Na*and its C=:O bond,which ensures a prior FEC decomposition in passivating the Na surface against other carbonate molecules.Further,by adopting cryogenic tranmission electron microscopy(cryo-TEM),we found that the Na filaments grow into substantially larger diameter from-400nm to>1 pum with addition of FEC upon the threshold value.A.highly crstalline and much thiner(-40 nm)slid-electrolyte interphase(SED)is consequently observed to uniformly wrap the Na surface,in contrast to the severely corroded Na as retrieved from the blank electrolyte.The potence of FEC is further demonstrated in a series of"corrosive solvents"such as ethy!l acetate(EA)。trimethyl phosphate(TMP),and actonitrile(AN)enabling highly reversible SMAs in the otherwise unusable solvent systems.展开更多
基金sponsored by the National Natural Science Foundation of China(NSFC Nos.21975186,51632001,and 22005334)supports from Natural Science Foundation of Beijing(grant No.Z200013).
文摘Sodium metal anodes(SMAs)sufer from extremely low reversibility(<20%)in carbonate based clectrolytes-this piece of knowledge gained from previous studics has ruled out the application of carbonate solvents for sodium metal batteries.Here,we overturn this conclusion by incorporating fluoroethylene carbonate(FEC)as cosolvent that renders a Na plating/stripping fficiency of>95%with conventional NaPF。salt at a regular concentration(1.0M).The peculiar role of FEC is firstly.unraveled via its involvement into the solvation structure,where a threshold FEC concentration with a coordination number>1.2 is needed in guaranteeing high Na reversibility over the long-term.Specifially,by incorporating an average number of 1.2 FEC molecules into the primary Na*solvation sheath,lowest unoccupied molecular orbital(LUMO)levels of such Nat-FEC solvates undergo further decrease,with spin electrons residing either on the O=C 0(O)moiety of FEC or sharing between Na*and its C=:O bond,which ensures a prior FEC decomposition in passivating the Na surface against other carbonate molecules.Further,by adopting cryogenic tranmission electron microscopy(cryo-TEM),we found that the Na filaments grow into substantially larger diameter from-400nm to>1 pum with addition of FEC upon the threshold value.A.highly crstalline and much thiner(-40 nm)slid-electrolyte interphase(SED)is consequently observed to uniformly wrap the Na surface,in contrast to the severely corroded Na as retrieved from the blank electrolyte.The potence of FEC is further demonstrated in a series of"corrosive solvents"such as ethy!l acetate(EA)。trimethyl phosphate(TMP),and actonitrile(AN)enabling highly reversible SMAs in the otherwise unusable solvent systems.
