Aqueous zinc metal batteries have significant potential for use in portable devices and large-scale energy storage systems.1 Nevertheless, the growth of zinc dendrites and parasitic reactions worsen the stability of zinc metal electrodes.2 Therefore, strategies must be found to prevent zinc dendrites and other unfavorable reactions. In this study, we develop a macromolecular crowding electrolyte (MCE) by using polyvinylpyrrolidone (PVP) as a crowding agent. The strong hydrogen bonds between PVP and H2O molecules effectively suppress water activity, resulting in an enlarged electrochemical stability window and wide operating temperatures (−20 to 50 °C). Furthermore, the adsorption of PVP on the electrode surface enables progressive nucleation in the MCE, providing promising reversibility and long-term stability during the zinc plating/stripping process. More importantly, the deep insights into Zn deposition morphology and crystallinity illustrate the crystallographic reorientation into (100) and (101) facets, exhibiting vertical and uniform zinc deposition. Density functional theory calculations confirm that the preferential exposure of crystal facets is due to the adsorption of PVP molecules on the zinc metal surface. Furthermore, the electrochemical tests employing a rotating disc electrode and a three-electrode system demonstrate the notable mass transfer limitation in the MCE, which mainly contributes to the reoriented zinc deposition. The vertical arrangement of deposited zinc is more beneficial than parallel deposition to contact the ions outside the depletion region to overcome mass transfer limitation in the MCE. As a consequence, the preferential zinc deposition by exposing (100) and (101) facets enables Zn/Zn symmetric cells to cycle for over 3000 hours at different current densities. Additionally, Na0.33V2O5/Zn and MnO2/Zn full cell batteries in MCE exhibit favorable cycling stability and capacity across a wide temperature range from −20 to 50 °C. This work unveils a unique approach to reorienting the preferential crystallography of deposited zinc, providing a new direction to regulate and control the favorable orientation of zinc deposition.
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