NH₄⁺ Charge Carrier Coordinated H‐Bonded Organic Small Molecule for Fast and Superstable Rechargeable Zinc Batteries

Organic small molecules as high-capacity cathodes for Zn-organic batteries have inspired numerous interests, but are trapped by their easy-dissolution in electrolytes. Here we knit ultrastable lock-and-key hydrogen-bonding networks between 2, 7-dinitropyrene-4, 5, 9, 10-tetraone (DNPT) and NH₄ ⁺ charge carrier. DNPT with octuple-active carbonyl/nitro centers (H-bond acceptor) are redox-exclusively accessible for flexible tetrahedral NH₄ ⁺ ions (H-bond donator) but exclude larger and rigid Zn²⁺ , due to a lower activation energy (0.14 vs. 0.31 eV). NH₄ ⁺ coordinated H-bonding chemistry conquers the stability barrier of DNPT in electrolyte, and gives fast diffusion kinetics of non-metallic charge carrier. A stable two-step 4e⁻ NH₄ ⁺ coordination with DNPT cathode harvests a high capacity (320 mAh g⁻¹ ), a high-rate capability (50 A g⁻¹ ) and an ultralong life (60,000 cycles). This finding points to a new paradigm for H-bond stabilized organic small molecules to design advanced zinc batteries.