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Batteries 2022, 8, 272 15 of 20 Batteries 2022, 8, x FOR PEER REVIEW 15 of 19 3. Summary and Perspective In this review, we summarized the signs of progress of AFSMBs, focusing on the In this review, we summarized the signs of progress of AFSMBs, focusing on the optimization strategies of the electrolytes, interfaces, and current collectors. Figure 9 sum- optimization strategies of the electrolytes, interfaces, and current collectors. Figure 9 sum- marizes the objectives of this review article, which also presents the current strategies con- marizes the objectives of this review article, which also presents the current strategies cerning electrolyte chemistry, SEI, and current collectors. In the electrolyte section, we concerning electrolyte chemistry, SEI, and current collectors. In the electrolyte section, we comprehensively compared the development of ester−based or ether-based electrolytes. comprehensively compared the development of ester–based or ether-based electrolytes. It It is important to note that pure carbonate solvents tend to react with sodium metal. As a is important to note that pure carbonate solvents tend to react with sodium metal. As a result, when using ester−based electrolytes in AFSMBs, film-forming chemicals are re- result, when using ester–based electrolytes in AFSMBs, film-forming chemicals are required quired to stabilize the pure carbonate solvents. In particular, the sodium-based electro- to stabilize the pure carbonate solvents. In particular, the sodium-based electrolytes can lytes can benefit from the PC’s high permittivity and reduced melting and higher boiling benefit from the PC’s high permittivity and reduced melting and higher boiling points, points, while boosting SEI growth with minimal amounts of cosolvents or additives. This while boosting SEI growth with minimal amounts of cosolvents or additives. This is benefi- is beneficial to the development of electrolytes with comprehensive performances. In ad- cial to the development of electrolytes with comprehensive performances. In addition, the dition, the corrosion reaction of the fluorinated solvents, salts, and additive electrolytes corrosion reaction of the fluorinated solvents, salts, and additive electrolytes with sodium with sodium metal anodes has sparked renewed interest in non−corrosive electrolytes for metal anodes has sparked renewed interest in non–corrosive electrolytes for AFSMBs. An AFSMBs. An alternative option is to utilize an ether−based electrolyte or an ionic liquid alternative option is to utilize an ether–based electrolyte or an ionic liquid electrolyte. We electrolyte. We also emphasized that the ether-based electrolyte design should consider the also emphasized that the ether-based electrolyte design should consider the electrolyte electrolyte potential window, especially for those high-voltage cathodes. Strategies such as potential window, especially for those high-voltage cathodes. Strategies such as concen- concentrated electrolytes or localized concentrated electrolytes are options for addressing this trated electrolytes or localized concentrated electrolytes are options for addressing this concern. Ionic liquid electrolytes have also been widely used for SMBs. However, there are concern. Ionic liquid electrolytes have also been widely used for SMBs. However, there currently few relevant references reported for AFSMBs. In the future, strategies on the electro- are currently few relevant references reported for AFSMBs. In the future, strategies on the lytes for AFSMBs may be divided into three major categories: (i) the development of novel electrolytes for AFSMBs may be divided into three major categories: (i) the development of ether−based electrolytes; (ii) quantifying the capacity loss mechanism of the inactive sodium novel ether–based electrolytes; (ii) quantifying the capacity loss mechanism of the inactive metal; and (iii) paying special attention to the electrolyte operating temperature. sodium metal; and (iii) paying special attention to the electrolyte operating temperature. Figure 9. Summary of the current strategies concerning electrolyte chemistry, SEI, and current collectors. Figure 9. Summary of the current strategies concerning electrolyte chemistry, SEI, and current collectors. The nature of SEIs in AFSMBs were also introduced in terms of the in situ formed SEI and the artiffiicial SEI. We mentioned that the SEI layer can be designed by regulating the sodium salts, additives, solvents, and concentration of the electrolytes. The carbonate electrolyte tends to react with the sodium metal, so we should particularly pay attention to electrolyte tends to react with the sodium metal, so we should particularly pay attention this when selecting the carbonate solvents. Some additives are strongly recommended for to this when selecting the carbonate solvents. Some additives are strongly recommended for the formation of a passivation film to protect the deposited sodium metal. Because ofPDF Image | Anode-Free Rechargeable Sodium-Metal Batteries
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