Saturation absorbed sodium benzenesulfonate as crystallization modulating additive for dendrite-free Zn anode

• The concentration of SBS additive plays a significant role in enhancing the performance of zinc metal batteries . • The sulfonate groups in SBS vertically adsorbed on zinc surface can construct a top-down internal electric field. • SBS shows selective adsorption on Zn (002) crystal face and regulates the growth of stacked (002)-textured Zn. • SBS enhances the reversibility of zinc plating//stripping (over 4000 cycles). Aqueous Zn metal batteries face significant obstacles such as rampant Zn dendrite growth and side reactions besides their benefits. Adding trace amounts of organic additives in electrolyte is considered as an application strategy to achieve long cycling performance. In this study, sodium benzenesulfonate (SBS) composed of an electron-withdrawing sulfonate group and a benzene ring is introduced as a crystallization modulating additive into ZnSO 4 solution. We find that the saturation absorption concentration of SBS plays a key role in realizing the uniform deposition of Zn metal anode. SBS is vertically adsorbed onto Zn surface, building a top-down internal electric field that promotes the three-dimensional diffusion of Zn 2+ . SBS shows a crystallization modulating behavior in terms of grain nucleation, grain morphology and crystal orientation. The well-tailored crystallization structure contributes to a uniform Zn metal deposition for long cycling, which improved from 300 to 4000 cycles with the addition of SBS. At the saturation concentration of SBS, the Zn||Zn symmetric cell shows a lifespan of over 2200 h at 1 mA cm −2 . This work not only provides a new option for Zn metal batteries additives but also offers new insights into the function of electrolyte additives.