Electron-Induced Molecular Programming Drives Interfacial Chemistry for Ah-Level Zinc Batteries.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 41877427.
- Also identified by DOI 10.1002/adma.72891 and PMC identifier 13103630.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Solid-electrolyte interphases (SEIs) are essential for stabilizing metal anodes in aqueous zinc (Zn) batteries (AZBs), yet their formation remains intrinsically uncontrolled, leaving the interphase vulnerable to dissolution and water-driven parasitic reactions. Herein, we report an electron-induced molecular programming strategy that uses only 1 mM of 4-bromobenzenediazonium tetrafluoroborate (BDTF) to in situ construct a Zn<sup>2+</sup>-favored molecular lock on the ZnF<sub>2</sub>-rich SEI surface. Electrochemically generated p-bromoaniline becomes molecularly woven into the inorganic layer, forming an ultrathin molecular-lock shell (∼1 nm) atop a graded hybrid SEI. Through N-Zn coordination coupled with Br-induced interfacial polarization, the molecular lock reorganizes the local electrostatic environment, stabilizes ZnF<sub>2</sub>, limits water access, and promotes desolvation-facilitated Zn<sup>2+</sup> transport. As a result, the programmed SEI enables highly reversible Zn plating/stripping with a 99.8% average Coulombic efficiency, and stable cycling under 80% depth of discharge at 10 mA cm<sup>-</sup> <sup>2</sup>. Moreover, it displays broad cathode compatibility, extending cycling stability in vanadium-, manganese-, and iodine-based full cells. In Ah-level pouch cells with ultrahigh vanadium-based cathode loading (21 mg cm<sup>-2</sup>), the system delivers 1.2 Ah with 81% retention after 100 cycles, surpassing state-of-the-art aqueous Zn batteries that typically fail at high mass loading.