Aqueous zinc‐ion batteries are largely restricted by the unsatisfactory performance of zinc (Zn) anodes, including their poor stability and irreversibility. In particular, the mechanism behind the electrochemical contrast caused by the surface crystal plane, which is a decisive factor of the electrochemical characteristics of the hostless Zn anode, is still relatively indistinct. Hence, new insight into a novel anode with a surface‐preferred (002) crystal plane is provided. The interfacial reaction and morphology evolution are revealed by theoretical analysis and post‐mortem/operando experimental techniques, indicating that Zn anodes with more exposed (002) basal planes exhibit free dendrites, no by‐products, and weak hydrogen evolution, in sharp contrast to the (100) plane. These features benefit the Zn (002) anode by enabling a long cyclic life of more than 500 h and a high average coulombic efficiency of 97.71% for symmetric batteries, along with delivering long cycling stability and reversibility with life spans of over 2000 cycles for full batteries. This work provides new insights into the design of high‐performance Zn anodes for large‐scale energy storage and can potentially be applied to other metal anodes suffering from instability and irreversibility.

The development of low-cost and high-safety zinc-ion batteries (ZIBs) has been extensively discussed and reviewed in recent years, but the work on comprehensive discussion and perspective in developing zinc-ion electrolytes...

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Low‐cost and highly safe zinc‐manganese batteries are expected for practical energy storage and grid‐scale application. The electrolyte adjustment is further combined to boost their performance output; however, the mechanism behind the electrochemical contrast caused by electrolyte composition remains unclear, which has held back the development of these systems. Hence, new insight into the electrochemical activation of manganese‐based cathodes, which is induced by the aqueous zinc‐ion electrolyte, is provided. The relationship between the desolvation of Zn2+ from [Zn(OH2)6]2+‐solvation shell and the electrolyte/electrode interfacial reaction to form Zn4SO4(OH)6·4H2O phase or its analogues is established, which is the key for the electrochemical activation. Further electrolyte optimization promotes the cycling stability of Zn/LiMn2O4 battery with a long life span over 2000 cycles. This work illuminates the confused direction in exploring electrolyte for zinc‐manganese batteries.

Zn-based aqueous batteries (ZABs) have been regarded as promising candidates for safe and large-scale energy storage in the "post-Li" era. However, kinetics and stability problems of Zn capture cannot be concomitantly regulated, especially at high rates and loadings. Herein, a hierarchical confinement strategy is proposed to design zincophilic and spatial traps through a host of porous Co-embedded carbon cages (denoted as CoCC). The zincophilic Co sites act as preferred nucleation sites with low nucleation barriers (within 0.5 mA h cm −2 ), and the carbon cage can further spatially confine Zn deposition (within 5.0 mA h cm −2 ). Theoretical simulations and in situ/ ex situ structural observations reveal the hierarchical spatial confinement by the elaborated all-in-one network (within 12 mA h cm −2 ). Consequently, the elaborate strategy enables a dendrite-free behavior with excellent kinetics (low overpotential of ca. 65 mV at a high rate of 20 mA cm −2 ) and stable cycle life (over 800 cycles), pushing forward the next-generation high-performance ZABs.