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Batteries 2022, 8, 157 15 of 25 Batteries 2022, 8, 157 chemical window of 5.0 V and a transference number of 0.882 with electrical conductivity with a cathode and Na metal anode and a high capacity of 106 mAh g−1 could be received in the initial cycle with the Na3V2(PO4)3 cathode. To realize the all-solid-state Na metal batteries, inorganic–organic hybridization of solid-state electrolytes was one of the routes. Matios et al. reported a hybrid solid-state electrolyte with Na3Zr2Si2PO12 (NZSP), polypropylene carbonate (PPC), and PEO host (NZSP-PPC-PEO) [52]. They found that Na metal could turn PPC from a long chain poly- mer into shorter chain segments spontaneously, resulting in the formation of a highly conductive interfacial-wetting layer. Therefore, this phenomenon was utilized to formulate NZSP and PEO host by the content of PPC, as shown in Figure 6a. Due to the highly con- ductive interfacial-wetting layer, the interfacial conductivity of solid-state electrolytes could be remarkably improved, which resulted in the stable cycling performance (1000 h, 0.1 mA cm−2, 0.1 mAh cm−2) in the Na||Na symmetric battery. Ling et al. developed an inter- penetrating network of poly(ether-acrylate) (ipN-PEA) in NZSP ceramic/poly(vinylidene fluoride-hexafluoropropylene) (NZSP/PVDF-HFP) with sandwich structure (CESS) as a flexible solid-state electrolyte [116]. They found that this flexible solid-state electrolyte presented an excellent Na-ion transference number of 0.63 and a high ionic conductivity of 10−4 S cm−1. In the Na||Na symmetric battery, a low polarization voltage of ±50 mV after 400 h at 0.2 mA cm−2 was delivered in the CESS flexible solid-state electrolyte, which presented much better performance than that in liquid electrolytes. They suggested that the improved electrochemical performance of the Na metal anode in the CESS flexible solid-state electrolyte was due to the internal rigidity and external flexibility, resulting in the mitigation of interfacial ion transfer issues and the guarantee of mechanical strength. These behaviors would contribute to the inhibition of Na dendrite growth and dead Na formation. Yu et al. reported a synthetic strategy of NZSP ceramic microtubes with cotton fiber template [117]. After that, they used NZSP ceramic microtubes with poly(ethylene oxide) (PEO)-PVdF-HFP-NaClO4-1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EmimFSI) (NZSP/PPE) for hybridization to develop an inorganic-organic solid-state electrolyte. After hybridization, this type of solid-state electrolyte presented an electro- of 2.79 × 10 S cm −1 17 of 26 . Due to these characters, the inorganic-organic solid-state electrolyte −4 in the Na||Na symmetric battery could be cycling for 200 h at 0.05 mA cm−2. Figure 6. Cont.PDF Image | Recent Development for Sodium Metal Batteries
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