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current collector to load deposited sodium metal [84]. As illustrated in Figure 8a, a sodiophilic alloy of NaZn13 formed on the top of the zinc foil after the initial Na deposition. The results show that the nanoscale NaZn13 interface can significantly reduce the deposition overpo- Batteries 2022, 8, 272 14 of 20 tential of sodium metal and induce uniform and dense deposition of Na, thus improving the cycling stability and average CE of the Na metal anode. Furthermore, the nucleation overpotential profiles show that Zn foil stands out in Al, Fe, Mg, Ti, and Cu foils, indicat- as the current collector to load deposited sodium metal [84]. As illustrated in Figure 8a, a ing excellent sodiosopdhioilpichitliyc awlloiythofsNoadZinumfo(rFmigeduoren t8hbe )t.opAolfththoeuzginhc ftohiliasftwerothrekinciotinalsNtraudcetpsoasition. 13 The results show that the nanoscale NaZn interface can significantly reduce the deposition 13 promising sodiophilic alloy, their following cycling performance is still unsatisfactory. overpotential of sodium metal and induce uniform and dense deposition of Na, thus There are two unresolved issues. One is the initially formed sodiophilic alloy cannot main- improving the cycling stability and average CE of the Na metal anode. Furthermore, the tain its structure upon cycling; the volume expansion would result in the detachment from nucleation overpotential profiles show that Zn foil stands out in Al, Fe, Mg, Ti, and Cu foils, the current collectoinrd[i8c5at]i.nIgnexacdedlleitnitosno,dtiohpeheilxicpitoyswuirthesofdituhme a(Flilgouyrein8bt)h. Aelethleocutgrhotlhyitsewdoorkesconostructs a promising sodiophilic alloy, their following cycling performance is still unsatisfactory. solve the problem of the side reaction between the electrolyte and anode [86]. Guided by There are two unresolved issues. One is the initially formed sodiophilic alloy cannot theoretical simulations and real-time phase evolution, Bai et al. designed a series of me- maintain its structure upon cycling; the volume expansion would result in the detachment chanically flexible and ultralight medium/high−entropy alloys within the carbon nano- from the current collector [85]. In addition, the exposure of the alloy in the electrolyte tubes framework, i.e., Cu2NiZn@CNT, FeCoNiZn@CNT, and FeCoNiAlZn@CNT, acting does not solve the problem of the side reaction between the electrolyte and anode [86]. as the sodium dGeupiodesditiboynthecourertriceanl tsimcuollalteiocntos arsnd (reFailg-tuimre ph8acs)e e[v8o7l]u.tioAn,mBaoi netgal. tdheesmign, edtha eseries of mechanically flexible and ultralight medium/high–entropy alloys within the carbon Cu2NiZn@CNT current collector shows the lowest sodium deposition overpotential. As nanotubes framework, i.e., Cu2NiZn@CNT, FeCoNiZn@CNT, and FeCoNiAlZn@CNT, illustrated in Figure 6c, during the sodiumization process, the sodiophilic Zn atoms are acting as the sodium deposition current collectors (Figure 8c) [87]. Among them, the extracted from the cubic Cu2NiZn and anchored on Na+ to form the NaZn13 alloy. The Cu2NiZn@CNT current collector shows the lowest sodium deposition overpotential. As NaZn13 alloy migrailtleustaractceodridniFnigutroe 6thc,edcuorincgetnhtersaotdioiunmgizratdioiennptr.oTcehses, uthneisfodrmiopdhilsitcrZibnuatiomns are extracted from the cubic Cu NiZn and anchored on Na+ to form the NaZn alloy. The and diffusion of sodiophilic sites inside CN2 Ts can theoretically maximize the Na a1f3finity NaZn13 alloy migrates according to the concentration gradient. The uniform distribution of CNT scaffolds while avoiding particle agglomeration, volume expansion, and direct contact corrosion with electrolytes. and diffusion of sodiophilic sites inside CNTs can theoretically maximize the Na affinity of CNT scaffolds while avoiding particle agglomeration, volume expansion, and direct contact corrosion with electrolytes. Figure 8. Illustration of the strategies for constructing sodiophilic alloys. (a) Schematic diagram Figure 8. Illustration of the strategies for constructing sodiophilic alloys. (a) Schematic diagram of of the Na deposition behavior at first and the subsequent cycles on the bare Cu foil and Zn foil; the Na deposition behavior at first and the subsequent cycles on the bare Cu foil and Zn foil; (b) the (b) the sodium deposition voltage profiles on the different current collectors at current density of sodium deposition voltage profiles on the different current collectors at current density of 1.0 mA 1.0 mA cm−2 [84]; copyright 2022, IOP Publishing. (c) Illustration of the Na deposition mechanism cm−2 [84]; copyright 2022, IOP Publishing. (c) Illustration of the Na deposition mechanism within within the Cu2NiZn@CNT substrate [87]. Reproduced with the permission of ref. [87], Royal Society the Cu2NiZn@CNT substrate [87]. Reproduced with the permission of ref. [87], Royal Society of Chemistry, copyright 2022. 3. Summary and Perspective of Chemistry, copyright 2022.PDF Image | Anode-Free Rechargeable Sodium-Metal Batteries
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