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Batteries 2022, 8, 157 8 of 25 based electrolytes to enhance the electrochemical performance of the Na metal anode [63]. They found that TMTD could in situ generate a stable SEI layer as an interfacial protection layer on the Na metal surface. According to the constituent analysis, the SEI layer was constituted by the rich organic sulfide salts, which could be more conducive to maintaining the stability of the Na metal anode during the stripping/plating process. In addition, it was found that a very high CE of 94.25% could be delivered and the full battery also achieved a high reversible capacity of 86.2 mAh g−1 after 600 cycles at 4 C. For the Na metal anodes, Na dendrite growth would lead to separator puncture, which triggered the combustion events of the battery. Therefore, the exploitation of non- inflammable electrolytes also was a pursuit direction for NMBs. Yi et al. designed a low-flammable electrolyte, which consisted of 1 M NaPF6 in DME, FEC, and 1,1,1,3,3,3- hexafluoroisopropylmethyl ether (HFPM) with a volume ratio of 2:1:2 (denoted as NaPF6- FRE) for NMBs [77]. They found that Na||Na symmetric battery in NaPF6-FRE electrolyte exhibited a superior cycling performance for 800 h with a stable voltage profile (1 mA cm−2, 1 mAh cm−2), which was much higher than that of the Na||Na symmetric battery in electrolyte without an HFPM (1 M NaPF6 in DME/FEC) electrolyte. They suggested that the addition of HFPM would generate a new F-containing SEI layer, which could stabilize the Na metal surface. In addition, the NaPF6-FRE electrolyte also presented a wide electrochemical window of 5.2 V. Zheng et al. utilized superior miscibility of all-fluoride fire extinguishant into fluorinated carbonate electrolytes (N-FEPH + P) for NMBs [78]. Considering the addition of an all-fluoride fire extinguishant in the electrolyte, the flaming fire was also quenched in the N-FEPH-P electrolyte. With the all-fluoride fire extinguis- hant, the Na||Na symmetric battery performance in the N-FEPH + P electrolyte could greatly improve. The cycle of 1100 h at 1.0 mAh cm−2 and 800 h at 5.0 mAh cm−2 could be received in Na||Na symmetric battery with N-FEPH + P electrolyte. After matching the Na3V2(PO4)2O2F cathode, the full battery also presented a high initial CE of 94.7% and capacity retention of 87.1% after 1000 cycles at 0.5 C. After disassembling the battery, they found that a thin F-rich SEI layer was established on both the Na metal anode and the cathode in the N-FEPH + P electrolyte, which facilitated the efficient Na metal plat- ing/stripping and enhanced the cycle life of over 1000 cycles in full batteries. As one low dielectric constant and highly fluorinated and intrinsically nonflammable ether, 1,1,2,2- tetra-fluoroethyl 2,2,3,3-tetrafluoropropyl ether (HFE) and trimethyl phosphate (TMP) were also considered for used in electrolyte for NMBs. Liu et al. introduced two functional fluorinated solvents of HFE and FEC into the TMP-based electrolyte for NMBs [79]. Under the flame burning, the electrolyte-soaked separator still had not ignited, indicating that this type of TMP-FEC-HFE-based electrolyte was fire resistant. For NMBs, the Na||Na symmetric battery presented the cycle for 800 h at 1.0 mA cm−2 or 3.0 mAh cm−2. They also suggested that the non-solvating HFE plays a critical role in local electrolyte concentration to decrease the unfavorable decomposition of TMP. From the aforementioned discussion, we also summarized the important parameters, including electrolyte constituents, cycling stability, and full battery performance of liquid electrolyte recently reported NMBs in Table 1.PDF Image | Recent Development for Sodium Metal Batteries
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