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Batteries 2022, 8, 157 12 of 25 Polymer Electrolytes POSS-4PEG2K PSP-GPE PTMC-NaFSI ETPTA-NaClO4 -QSSE PEO-Cu-MOF IL-MOF BC-TEP/VC/NaClO4 GO-PVDF-HFP NaPTAB-SGPE SILGM Ionic Conductivity (mS cm−1)@Temperature (◦C) 4.5 × 10−3@30 0.1@RT 0.05@25 1.2@RT 3.48@RT 0.36@RT 0.22@RT 2.3@RT 0.094@RT 2@23 Symmetrical Cell (Cycle Performance (h)@Current Density (mA cm−2)) 3550@0.5 620@1 / 1000@0.1 1000@0.2 500@1 / 400@5 100@0.05 / Full Cell (Cathode@Capacity (mAh g−1)@Current Density (C)) NaxV2O5@305@0.05 Na3 V2 (PO4 )3 @89.1@0.2 Prussian blue@90@0.2 Na3 V2 (PO4 )3 @101@1 NaCrO2 @120.7@0.1 Na3 Ni1.5 TeO6 @83.8@0.1 Na3 V2 (PO4 )3 @84.3@0.2 Na3 V2 (PO4 )3 @107@1 Na3 V2 (PO4 )3 @90.3@0.05 Na3 V2 (PO4 )3 @81.7@0.1 References [96] [97] [98] [99] [100] [104] [101] [102] [105] [106] In addition, some functional polymer solid-state electrolytes were also being investi- gated. Yang et al. used poly(methyl vinyl ether-alt-maleic anhydride) (P(MVE-alt-MA)) as the polymer host, bacterial cellulose (BC) as the reinforcement, and triethyl phosphate (TEP)/vinylene carbonate (VC)/NaClO4) as a plasticizer to obtain the polymer electrolyte (BC-TEP/VC/NaClO4) for NMBs [101]. They found that polymer electrolyte presented flame retardancy due to the addition of TEP (Figure 4f). In addition, an electrochemical win- dow of 4.4 V could also be received. As the polymer electrolyte for NMBs, Na3V2(PO4)3/Na full batteries exhibited an 84.4% capacity retention after 1000 cycles, which was much better than that of the full battery in the liquid electrolyte. Furthermore, the polymer electrolyte also provided an 84.8% capacity retention after 50 cycles at −10 ◦C in Na3V2(PO4)3/Na full batteries. Luo et al. developed a polymer electrolyte constituted by graphene oxide (GO) and PVDF-HFP with a high mechanical property and found that the 2 wt%GO-PVDF- HFP presented the highest Young’s modulus of 2.5 GPa and high ionic conductivity of 2.3 mS cm−1 (Figure 4g,h) [102]. The high mechanical property of polymer electrolytes could suppress the Na dendrite growth and avoid puncture by the Na dendrite. As result, the Na||Na symmetric battery in 2 wt%GO-PVDF-HFP electrolyte exhibited an ultra-long cycling performance over 400 h at 5 mA cm−2. Solid-state Na-O2 batteries had been regarded as promising energy storage devices due to their high energy density, ultralow overpotential, and abundant resources. Chen et al. reported a quasi-solid-state polymer electrolyte (QPE) composed of poly(vinylidene fluoride–co-hexafluoropropylene)-4% SiO2-NaClO4-tetraethylene glycol dimethyl ether (TEGDME) for high-performance Na-O2 batteries [103]. The abundant fluorocarbon chains of QPE played an important role in Na+-ion transfer, resulting in a high ionic conductivity of 1.0 mS cm−1. The Na-O2 batteries exhibited negligible voltage decay after cycling for 80 cycles at a cutoff discharge capacity of 1000 mAh g−1. After the aforementioned discussion, we also summarized the important parameters, including electrolyte constituents, cycling stability, and full battery performance of polymer electrolyte recently reported NMBs in Table 2. Table 2. Electrochemical properties of different polymer electrolytes in NMBs. 4. All-Solid-State Electrolytes for Na Metal Anodes Except for polymer electrolytes, the scientists also were looking at the all-solid-state electrolytes for NMBs. As the all-solid-state electrolytes in NMBs, several essential require- ments needed to be met: (1) possessing high ionic conductivity of above 10−4 S cm−1 at RT; (2) possessing a high ionic transference number; (3) possessing negligible conductivity; and (4) possessing a wide electrochemical window. Based on these essential requirements, the scientists set out to develop all-solid-state electrolytes for NMBs. Borrowed from a Li metal all-solid-state electrolyte, Na-β”-Al2O3 first received re- search attention from scientists [107–109]. Wen et al. explored the viability and stability of Na3PS4 and Na-β”-Al2O3 for NMBs [110]. They found that the Na3PS4 and Na-β”-Al2O3PDF Image | Recent Development for Sodium Metal Batteries
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