Rational Molecular Design of Redox‐Active Carbonyl‐Bridged Heterotriangulenes for High‐Performance Lithium‐Ion Batteries

Abstract Carbonyl aromatic compounds are promising cathode candidates for lithium‐ion batteries (LIBs) because of their low weight and absence of cobalt and other metals, but they face constraints of limited redox‐potential and low stability compared to traditional inorganic cathode materials. Herein, by means of first‐principles calculations, a significant improvement of the electrochemical performance for carbonyl‐bridged heterotriangulenes (CBHTs) is reported by introducing pyridinic N in their skeletons. Different center atoms (B, N, and P) and different types of functionalization with nitrogen effectively regulate the redox activity, conductivity, and solubility of CBHTs by influencing their electron affinity, energy levels of frontier orbitals and molecular polarity. By incorporating pyridinic N adjacent to the carbonyl groups, the electrochemical performance of N‐functionalized CBHTs is significantly improved. Foremost, the estimated energy density reaches 1524 Wh kg⁻¹ for carbonyl‐bridged tri (3,5‐pyrimidyl) borane, 50% higher than in the inorganic reference material LiCoO₂, rendering N‐functionalized CBHTs promising organic cathode materials for LIBs. The investigation reveals the underlying structure‐performance relationship of conjugated carbonyl compounds and sheds new lights for the rational design of redox‐active organic molecules for high‐performance lithium ion batteries (LIBs).