Promising aqueous zinc metal batteries (AZMBs) continue to face significant challenges regarding zinc anode reversibility due to detrimental reactions including hydrogen evolution and corrosion. Herein, the d-band center is used as an “intuitive descriptor” to compare the hydrogen evolution activity of zinc-based transition bimetallic oxides (ZTBOs) of fourth-period transition metal elements, and the advantages of ZnTi₃O₇ (ZTO) functional protective layer in inhibiting hydrogen evolution and extending the lifespan of the zinc anode are selectively identified. The ZTO exhibits a lower d-band energy level, which affects the adsorption of active H* and exhibits lower hydrogen evolution reaction activity. At the same time, the dense ZTO protective layer provides suitable ion channels to promote the uniform distribution of zinc flux and achieve uniform Zn deposition. Thus, cells with Zn@ZTO anodes exhibit over 6000 h of cycling stability (1 mA cm⁻²) and a high coulombic efficiency of 99.9% within 1200 cycles. Moreover, when paired with a V₆O₁₃ cathode, the assembled full cell exhibits excellent lifespan, retaining 86.9% of its capacity after 5000 cycles at 10 A g⁻¹. This work provides new strategies and insights for designing inorganic protective layers, addressing HER-related challenges, and advancing the practicality of AZMBs.

The energy storage behaviors of MnO₂ for aqueous Zn-MnO₂ batteries mainly depend on the Zn²⁺/H⁺ intercalation but are limited by poor ion/electron migration dynamics and stability. Herein, a strategy is proposed that promoting proton migration kinetics ameliorates H⁺ storage activity by introducing Ni²⁺ into γ-MnO₂ (Ni-MnO₂). Ni²⁺ can lower the diffusion barrier of H⁺ and selectively induce the ion intercalation, thereby alleviating the electrostatic interaction with the lattice. Moreover, Ni²⁺ enables the adjacent [MnO₆] octahedrons to have better electron conductivity. The Ni-MnO₂ exhibits superior rate performance (nearly four times specific capacity compared with MnO₂) and ultra-long-cycle stability (100% of capacity retention after 11000 cycles at 3.0 A g⁻¹). The calculation indicates that the Ni-MnO₂ allows H⁺ migrate rapidly along the one-dimensional tunnel due to reduction of the activation energy caused by Ni²⁺ regulating, thus achieving excellent reaction kinetics. This work brings great potential for the development of high-performance aqueous Zn-MnO₂ batteries.

High-rate battery-type cathode materials have attracted wide attention for advanced battery-supercapacitor hybrid (BSH) devices. Herein, a core-shell structure of the hollow mesoporous carbon spheres (HMCS) supported NiSe₂ nanosheets (HMCS/NiSe₂) is constructed through two-step reactions. The HMCS/NiSe₂ shows a max specific capacity of 1,153.5 C·g^-1 at the current density of 1 A·g^-1, and can remain at 774.5 C·g^-1 even at 40 A·g^-1 (the retention rate as high as 67.1%) and then the HMCS/NiSe₂ electrode can keep 80.5% specific capacity after 5,000 cycles at a current density of 10 A·g^-1. Moreover, the density functional theory (DFT) calculation confirmed that the introduction HMCS into NiSe₂ made adsorption/desorption of OH^- easier, which can achieve higher rate capability. The HMCS/NiSe₂//6 M KOH//HMCS hybrid device has energy density of 47.15 Wh·kg^-1 and power density of 801.8 W·kg^-1. This work provides a feasible electrode material with a high rate and its preparation method for high energy density and power density energy storage devices.