Abstract

Abstract The design of electrode compatible with wide‐temperature, fast‐charging, and long‐lifespan aqueous zinc‐ion batteries is a great challenge that urgently needs addressing. However, the mismatch between runaway host dissolution and high interfacial hydrophilicity within electrode is a contradictory problem that restricts their electrochemical performance. In this report, take the typical vanadium diselendie (VSe 2 ) host for example, by employing the natural polymer bacterial cellulose (BC) as the multifunctional mediator, a design paradigm of self‐assembly hybrid electrode with efficient tandem electrochemistry is presented. Theoretical and experimental research confirmed that such BC‐mediated hybrid structure exhibits multiple functions to well balance the cathode dissolution and storage kinetics. Impressively, such an electrode displayed an excellent rate capability (1–50 A g −1 ), and an unexpected record‐lifespan of 45 000 cycles. Beyond that, it also shows a good temperature‐tolerance ability, remaining the high specific capacities of 120 and 288 mAh g −1 (at 10 A g −1 ) after 3000 cycles at −25 and 50 °C, respectively. Note that such approach is also applicable to the high‐voltage platform MnO 2 and I 2 hosts, demonstrating its potential for universality. This discovery can provide a new design principle of robust electrode for advanced aqueous zinc‐ion batteries.