Engineering π‐Electron Bridge Enables Low‐Potential 2D Redox Polymer Anodes for High‐Voltage Aqueous All‐Organic Batteries

Abstract Aqueous all‐organic batteries (AAOBs) have emerged as a hot topic but their development was plagued by limited choices of anode materials, generally facing an intractable trade‐off between low potential and high stability. Here, we propose a novel π‐electron bridge engineering strategy to explore a class of 2D dioxin‐bridged redox covalent organic polymer (RCOP) as trade‐off‐breaking anodes for high‐voltage AAOBs. By establishing a tunable RCOP platform, we perform theoretical study to scrutinize how bridge units between active sites affect the electrode potential and redox activity for the first time. We discover that compared to common pyrazine bridge, the weakened conjugation and strong electron donor character of the proposed dioxin bridge can induce elevated LUMO level and enriched π‐electron populations in active sites, heralding a low electrode potential and enhanced redox activity. Besides, the nonaromaticity‐induced molecular flexibility of dioxin bridge mitigates intermolecular stacking for sufficient active sites exposure. To experimentally corroborate this, a new dioxin‐bridged 2D RCOP (D‐HATN) and its pyrazine‐bridged analogue (P‐HATN) are synthesized for proof‐of‐concept demonstration. D‐HATN displays excellent compatibility with Na + /Zn 2+ /NH 4 + /H 3 O + and obviously lower redox potentials in various dilute electrolytes compared to P‐HATN and most reported organic anodes, while featuring rapid Grotthuss‐type proton conduction and unprecedented durability in acid – 91.8 % capacity retention after 20000 cycles. Thus, the D‐HATN‐involved all‐organic proton battery delivers an average output voltage of 0.75 V, which can be further elevated to 1.63 V with alkaline‐acidic hybrid electrolyte design, affording markedly‐increased specific energy.