density. Therefore, developing highcapacity anode and cathode materials or new battery systems have drawn extensive attentions. [6,[21][22][23][24][25][26][27][28] Metal anodes, especially those with high-capacity and low-cost are promising alternative anode materials for LIBs in replace of graphite anode. [29][30][31][32][33][34] Generally, the metal anodes electrochemically alloy/ de-alloy with Li + to complete the battery reaction, which can store more energy than the intercalation/deintercalation mechanism in graphite. Table 1 displays the electrochemical properties of typical metallic anodes (Al, Sn, Zn, Mg, Sb, and Bi) with Li and graphite for comparison. While the graphite anodes suffer from low capacity (372 mA h g −1 ) and Li anodes suffer from severe safety issues caused by lithium dendrites, these metal anodes have many advantages in terms of high theoretical capacities, moderate operation potential for less dendrites formation, high abundance and low cost. [35] For example, aluminum has high theoretical capacity (993 mA h g −1 or 1411 mA h cm −3 for LiAl) with moderate potential plateau (≈0.38 V vs Li + /Li). [35,36] Considering both of the capacity increase and voltage drop by using metal anodes in a LIB model, Obrovac et al. calculated the volumetric energy increase in comparison to graphite based commercial battery (Table 1). [37] In such a model, the volumetric energy densities could be increased by different extents ranging from 10-42% when metal anodes were used. It is worth noticing that some recent studies have raised the idea of directly using metal foil as active anode material and simultaneously current collector. [38,39] This strategy can eliminate the usage of binder and conductive carbon black for anode preparation, simplify the battery processing steps, and also increase the loading amount of active materials, thus further enhancing the energy density and reducing the battery prices.While the metal anodes show good potential for application in high-performance LIBs, the main challenge for these metallic anodes is their large volume change caused by lithiation/delithiation process during cycling. [37,40,41] As the lithiation proceeds more deeply, the volume change becomes more severely for alloying anodes. For instance, the volume change of Sn (260%, Li 4.4 Sn) is larger than Al (97%, LiAl). The huge volume change could cause crack and pulverization of metal anodes, resulting in quick capacity decay and short cycling life. [42][43][44][45][46] Besides, metallic anode materials usually exhibited high first-cycle capacity loss due to their high reactivity withThe ever-growing market of portable electronic devices and electric vehicles has significantly stimulated research interests on new-generation rechargeable battery systems with high energy density, satisfying safety and low cost. With unique potentials to achieve high energy density and low cost, rechargeable batteries based on metal anodes are capable of storing more energy via an alloying/de-alloying process, in comparison to tradi...