Noninterference Revealing of “Layered to Layered” Zinc Storage Mechanism of δ‐MnO 2 toward Neutral Zn–Mn Batteries with Superior Performance

Abstract MnO 2 is one of the most studied cathodes for aqueous neutral zinc‐ion batteries. However, the diverse reported crystal structures of MnO 2 compared to δ‐MnO 2 inevitably suffer a structural phase transition from tunneled to layered Zn‐buserite during the initial cycles, which is not as kinetically direct as the conventional intercalation electrochemistry in layered materials and thus poses great challenges to the performance and multifunctionality of devices. Here, a binder‐free δ‐MnO 2 cathode is designed and a favorable “layered to layered” Zn 2+ storage mechanism is revealed systematically using such a “noninterferencing” electrode platform in combination with ab initio calculation. A flexible quasi‐solid‐state Zn–Mn battery with an electrodeposited flexible Zn anode is further assembled, exhibiting high energy density (35.11 mWh cm −3 ; 432.05 Wh kg −1 ), high power density (676.92 mW cm −3 ; 8.33 kW kg −1 ), extremely low self‐discharge rate, and ultralong stability up to 10 000 cycles. Even with a relatively high δ‐MnO 2 mass loading of 5 mg cm −2 , significant energy and power densities are still achieved. The device also works well over a broad temperature range (0–40 °C) and can efficiently power different types of small electronics. This work provides an opportunity to develop high‐performance multivalent‐ion batteries via the design of a kinetically favorable host structure.