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Batteries 2022, 8, 157 14 of 25 Figure 5. (a) Schematic configuration of Na||Na symmetric battery; (b) comparison of EIS of the Na Figure 5. (a) Schematic configuration of Na||Na symmetric battery; (b) comparison of EIS of the Na symmetric cells at RT and 80 °C with the cycling of 0, 128, and 330 h; (c) galvanostatic cycling of the symmetric cells at RT and 80 ◦C with the cycling of 0,–2128, and 330 h; (c) galvanostatic cycling of the Nasymmetriccellat80 °Cat0.25and0.50 mA cm ;thecorrespondingSEMimagesofYSZ-Na-β”- ◦ −2 Al2O3/Na interfaces at 80 °C with cycling times of (d) 0 h, (e) 128 h, and (f,g) 330 h, reproduced with Na symmetric cell at 80 C at 0.25 and 0.50 mA cm ; the corresponding SEM images of YSZ-Na-β”- permission from R◦eference [112] Copyright 2022, Springer Nature. (h) Surface, (i) cross-sectional Al2O3/Na interfaces at 80 C with cycling times of (d) 0 h, (e) 128 h, and (f,g) 330 h, reproduced with SEM images, and (j) enlarged cross-sectional SEM image of ANs-PVdF-HFP membranes, repro- permission from Reference [112] Copyright 2022, Springer Nature. (h) Surface, (i) cross-sectional duced with permission from Reference [114] Copyright 2019, Springer Nature. SEM images, and (j) enlarged cross-sectional SEM image of ANs-PVdF-HFP membranes, reproduced withpermissioInfardodmitRioenf,earneontchee[r1t1y4p]eCoofpalyl-rsioglhidt-2s0ta1t9e,eSlpecrtirnoglyerteNoaftuhereN. asuperionicconductors (NASICONs, Na3Zr2Si2PO12) ceramic electrolyte was also receiving great attention due to the high ionic conductivity and excellent electrochemical stability [53]. However, the pris- To further improve the performance of β”-Al2O3 in NMBs, Lei et al. designed a tine NASICON always exhibited a large interfacial resistance and poor interface wettabil- hybridization of inorganic ionic conductors and polymer electrolytes [114]. They used ity for the Na metal anode. Despite this, the scientists also found that they could improve a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)-based polymer to coat their performance by modifying NASICON solid-state electrolytes. Li et al. developed a β”-Al2O3 nanowires (ANs-PVDF-HFP) with uniform cross-linking. Figure 5h shows the method of direct growth of ultrathin graphene-like on the Na3Zr2Si2PO12 (G-NASICON) SEM images of the ANs-PVDF-HFP membrane. It was found that cross-linked β”-Al2O3 ceramic electrolyte, which could reduce the interfacial resistance and enable the Na-ion nanowires were embedded into the PVDF-HFP matrix. From the cross-sectional SEM image flux with homogeneousness across from the G-NASICON ceramic electrolyte to the Na (Figure 5i), the homogeneous and regular pores could be observed in the ANs-PVDF-HFP membrane. It was suggested that the homogeneous and regular pores could store the electrolyte, which was beneficial to shortening the Na-ion migration route and enhancing the ionic conductivity. In addition, the excellent contact and adhesion between the β”- Al2O3 nanowires and PVdF-HFP were also observed from the enlarged cross-sectional SEM image in Figure 5j. Due to this structure, the ANs-PVDF-HFP could provide dense and homogeneous Na-ion transportation channels, which facilitated the homogeneous Na metal deposition and decreased the growth of the Na dendrite. Therefore, when the Na3V2(PO4)3 cathode/Na full battery used ANs-PVDF-HFP as the electrolyte, very high capacity retentions of 95.3% and 78.8% after 1000 cycles at 1 C at 25 and 60 ◦C, respectively, were observed. In addition, another type of all-solid-state electrolyte of the Na superionic conductors (NASICONs, Na3Zr2Si2PO12) ceramic electrolyte was also receiving great attention due to the high ionic conductivity and excellent electrochemical stability [53]. However, the pris- tine NASICON always exhibited a large interfacial resistance and poor interface wettability for the Na metal anode. Despite this, the scientists also found that they could improve their performance by modifying NASICON solid-state electrolytes. Li et al. developed a method of direct growth of ultrathin graphene-like on the Na3Zr2Si2PO12 (G-NASICON) ceramic electrolyte, which could reduce the interfacial resistance and enable the Na-ion flux with homogeneousness across from the G-NASICON ceramic electrolyte to the Na metal anode [115]. Due to this modification, the Na||Na symmetric battery in G-NASICON ce- ramic electrolyte presented a stable cycle performance over 1000 h at 0.5 mA cm−2 with the capacity of 1 mAh cm−2. Due to the close interface contact, it was critical to the electrolytePDF Image | Recent Development for Sodium Metal Batteries
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