Aqueous alkaline rechargeable nickel‐zinc (Ni–Zn) batteries possess great potential for large‐scale energy storage systems because of their high output voltage, cheap cost, and intrinsic safety. However, the practical applicability of Ni–Zn batteries has been limited by traditional Ni‐based cathodes with low capacity and poor cycle stability. Rational design of electrode structure and composition is highly desired but still significantly challenging. Herein, uniform self‐supported hierarchical heterostructure composites interacting NiCo‐layered double hydroxide with 1D nickel sulfides heteronanowire rooted on Ni foam (NF\Ni3S2/NiS@NiCo‐LDH) are successfully developed by a hydrothermal sulfurization‐electrodeposition process. The self‐supported 3D hierarchical heterostructured composites nanoarray provides abundant reactive sites, rapid ion diffusion channels, and fast electron transfer routes, as well as strong structural stability. More significantly, the strong interfacial charge transfer between Ni3S2/NiS heteronanowire and NiCo‐LDH effectively modifies the electronic structure of the composites and thereby improving the reaction kinetics. Consequently, the NF\Ni3S2/NiS@NiCo‐LDH electrode presents a superior capacity of 434.5 mAh g−1 (1.73 mAh cm−2) at 3 mA cm−2. In addition, the fabricated NF\Ni3S2/NiS@NiCo‐LDH//Zn battery can offer a maximal energy density and power density as large as 556.3 Wh kg−1 and 26.3 kW kg−1, respectively, as well as an exceptional cycling performance.

AARBs development. However, although numerous studies have paid most attention to cathode materials, the development of anode materials is limited. [3] In most previous researches, Zn metal with high theoretical capacity (820 mA h g −1 ) was considered to be an anode material for AARBs. [4] Unfortunately, the Zn metal anode in alkaline electrolytes is inevitably burdened by dendrite growth and strong corrosion. [5] Additionally, iron or iron oxides are also chosen as anode materials for AARBs, but suffer from the low capacity and poor conductivity. [3f,6] To this end, the development of high-performance anode materials would hold great promise for AARBs.In the past few years, bismuth (Bi) metal has been noticed as a highly desirable anode material for AARBs by virtue of its high theoretical capacity (384.8 mAh g −1 ), reversible three-electron redox processes (Bi 0 /Bi 3+ ) and advantageous negative operating window in alkaline electrolytes. [3c,7] To date, various Bi-based materials were reported to optimize the performance. [8] In this regard, Zuo et al. first reported Bi electrode film on a Ti substrate as an encouraging anode for AARBs with high capacity of 170 mAh g −1 at current density of 0.5 A g −1 , yet the capacity only retained 60% after 90 cycles. [9] Further the cycling durability of Bi anode was optimized to more than 96% of after 10 000 cycles at 30 A g −1 by electrodepositing hierarchical single-crystalline Bi nanostructures on carbon cloth (CC), but with an inferior initial capacity of 96.2 mAh g −1 at 4.5 A g −1 . [10] After that, Zeng et al. prepared a 4D porous Bi nanoparticles/carbon structure to further optimize the electrochemical performance of Bi anodes, which in capacity was still only about 166.2 mAh g −1 at a current density of 0.47 A g −1 . What's more, although it yielded a remarkable 10 000 charge/ discharge cycles, the capacity was gradually declining. [11] Thus, advanced strategies are still looked forward to further boosting the new Bi anodes with both high capacity and stronger longterm durability.To date, surface carbon coating is regarded as a promising structure for electrodes, which has been widely studied in batteries, due to their merit of improving the electrode conductivity, [12] optimizing the surface chemistry of the active The aqueous alkaline rechargeable batteries (AARBs) have an attractive potential for electrochemical energy storage devices. In view of the advantages of high theoretical capacity and desirable negative operating window, bismuth (Bi) has been deemed as a hopeful anode material for AARBs. Unfortunately, intensive reported works of Bi anode are still confronted with limited capacity and poor cycling stability. Herein, the designed electrodes of different size Bi nanoparticles embedded in porous carbon nanofibers with a contrasting nitrogen doping content are obtained by electrospinning and thermal treatment processes. The effect of the N dopant in carbon shell is demonstrated on the Bi core, which is in favor of enhancing the capacity of Bi anode...