Dual-region synergistic modulation and (101) facet engineering for highly reversible zinc anodes
Shuai Zhang, Kittima Lolupiman, Dongdong Zhang, Zixuan Gao, Rungroj Chanajaree, Xinyu Zhang, Jin Cao, Jiaqian Qin
Abstract
Aqueous zinc-ion batteries (AZIBs) offer promising safety and affordability, but suffer from dendritic Zn growth and parasitic side reactions at the electrode-electrolyte interface. Herein, we construct a dual-region interfacial modulation framework by molecularly reconfiguring the Helmholtz double layer via trace methyl methacrylate (MMA). Exploiting its amphiphilic and functionally asymmetric architecture, MMA enables a coordinated interfacial reconstruction that disrupts Zn 2+ solvation in the outer Helmholtz plane, builds a chemisorbed coordination layer in the inner plane, and modulates local interfacial chemistry with spatial precision. This dual-region regulation collectively suppresses water reactivity, facilitates Zn 2+ desolvation, and drives crystallographically preferred deposition along the (101) plane, promoting lateral growth and mitigating dendrite formation. As a result, symmetric Zn||Zn cells exhibit over 4200 hours of stable cycling at 1 mA cm -2 and maintain 1100 hours of operation at 2 mA cm -2 , even at 0 °C. Zn||Ti half-cells achieve a Coulombic efficiency of 99.83%, while Zn||NH 4 V 4 O 10 full cells deliver 93.92% capacity retention after 400 cycles at 2 A g -1 , and preserve 85.3% after 300 cycles at 0 °C. This work demonstrates a scalable, mechanism-driven electrolyte design paradigm for dendrite-free and high-performance aqueous Zn metal batteries. MMA interacts with Zn 2+ in both the outer and inner Helmholtz planes, restructuring the electrolyte interface to enhance Zn 2+ desolvation and suppress parasitic reactions. Its unique molecular structure forms a stable coordination layer at the interface, reducing Zn 2+ hydration and promoting preferential deposition along the (101) crystal plane. This process effectively minimizes dendrite formation, enhancing the stability and reversibility of Zn anodes. • Methyl methacrylate (MMA) modulates both the outer and inner Helmholtz planes, suppressing parasitic side reactions. • MMA promotes preferential Zn deposition along (101) plane, enhancing lateral growth and minimizing dendrite formation. • Symmetric Zn||Zn cells exhibit over 4200 hours of stable cycling at 1 mA cm -2 and 1100 hours at 2 mA cm -2 , even under low-temperature conditions (0°C).