Enhanced Anion-Derived Inorganic-Dominated Solid Electrolyte Interphases for High-Rate and Stable Sodium Storage

It is highly desirable for the promising sodium storage possessing high rate and long stable capability,which are mainly hindered by the unstable yet conventional solvent-derived organic-rich solid electrolyte interphases.Herein,an electrolyte solvation chemistry is elaborately manipulated to produce an enhanced anion-derived and inorganic components-dominated solid electrolyte interphases by introducing a low permittivity(4.33)bis(2,2,2-trifluoroethyl)ether diluent into the sodium bis(trifluoromethylsulfonyl)imidedimethoxyethane-based high concentration electrolyte to obtain a localized high concentration electrolyte.The bis(2,2,2-trifluoroethyl)ether breaks the balance of original cation solvation structure and tends to interact with Na^(+)-coordinated dimethoxyethane solvent rather than Na^(+)in high concentration electrolyte,leaving an enhanced Coulombic interaction between Na^(+)and(FSO_(2))_(2)N^(-),and more(FSO_(2))_(2)N^(-)can enter the Na^(+)solvation shell,forming a further increased number of Na^(+)-(FSO_(2))_(2)N^(-)-dimethoxyethane clusters(from 82.0%for high concentration electrolyte to 94.3%for localized high concentration electrolyte)at a low salt dosage.The preferential reduction of this(FSO_(2))_(2)N^(-)-enriched clusters rather than the dimethoxyethane-dominated Na^(+)solvation structure produces an enhanced anion-derived and inorganic components-dominated solid electrolyte interphases.The reversible charge storage process of Na is decoupled by operando Raman along with a shift of D and G peaks.Benefiting from the enhanced anion-derived electrode-electrolyte interface,the commercial hard carbon anode in localized high concentration electrolyte shows a well rate capability(5 A g^(−1),70 mAh g^(−1)),cycle performance and stability(85%of initial capacity after 700 cycles)in comparison to that of high concentration electrolyte(68%)and low concentration electrolyte(only 5%after 400 cycles),indicative of uniqueness and superiorities towards stable Na storage.