Aqueous zinc-ion batteries (AZIBs) are promising large-scale energy storage devices, yet their practical application is severely restricted by cathode materials suffering from sluggish ion transport kinetics and poor cyclic stability. Organic polyaniline cathodes feature tunable redox sites and mechanical flexibility, but dense chain stacking and drastic volume expansion degrade their capacity and lifespan. Herein, we propose an electrostatic co-assembly and confined template polymerization strategy to fabricate mesoporous vanadium‑manganese polyoxometalate-intercalated polyaniline hybrid nanospheres (mPANI@POM). Negatively charged colloidal silica (SiO₂) serves as sacrificial templates to guide uniform adsorption of protonated aniline, while anionic POM clusters are electrostatically intercalated into polyaniline chains to form an organic–inorganic hybrid after template etching. The interconnected mesoporous framework shortens Zn²⁺/H⁺ diffusion paths, and the synergistic dual redox centers of conjugated polyaniline and multi-electron vanadium–manganese polyoxometalate greatly accelerate charge transfer. The mPANI@POM cathode achieves 264 mAh g^–1 at 0.5 A g^–1, retains 147 mAh g^–1 at 3.0 A g^–1, and exhibits good cycling stability with 90.6% capacity retention after 1000 cycles at 5.0 A g^–1. Combined in-situ characterizations verify that energy storage relies on synergistic reversible benzenoid–quinoid transformation and reversible V/Mn–O coordination evolution. This electrostatic co-assembly strategy offers a universal route to design high-performance organic–inorganic hybrid cathodes for durable AZIBs

Heterostructures composed of oxides and sulfides (nitrides or carbides) show great potential as sulfur host additives because of the strong adoptability of oxides and catalytic capability of sulfides towards the notorious lithium polysulfides (LiPSs). However, the migration and conversion pathway of LiPSs is seriously confined at a localized interface with inadequate active sites. In this work, the introduction of selenium vacancies into VSe_2−x has been demonstrated to successfully synergize the adsorbability and catalytic reactions of LiPSs at an integrated functional surface. The N-doped carbon nanosheets-assembled flower architectures embedded with selenium vacancy-rich VSe_2−x and partial vanadium oxides have been controllably synthesized and employed as the cathode additives for lithium-sulfur (Li-S) batteries. Both the experiments and first-principle calculations reveal their strong adsorption to LiPSs and their bidirectional catalytic functionality towards the conversion between S₈ and Li₂S. As expected, the charge and discharge kinetics of VSe_2−x containing sulfur cathodes is fundamentally improved (an outstanding rate capabilitiy with 693.7 mAh·g⁻¹ at 2 C, a remarkable long-term cyclability within 1,000 cycles at 2 C with S loading 2.27 mg·cm⁻², and an excellent areal capacity with 3.44 mAh·cm⁻² within 100 cycles at 0.5 C). This work presents an effective resolution to couple the adsorbability and catalytic reactions of LiPSs at the material design perspective, and the insights on bidirectional catalytic functionality are of vital to develop functional materials for advanced Li-S batteries.

High energy density and low-cost lithium-sulfur batteries have been considered as one of the most promising candidates for next-generation energy storage systems. However, the intrinsic problems of the sulfur cathode severely restrict their further practical application. Here, a unique double-shell architecture composed of hollow carbon spheres@interlayer-expanded and sulfur-enriched MoS_2+x nanocoating composite has been developed as an efficient sulfur host. A uniform precursor coating derived from heteropolyanions-induced polymerization of pyrrole leads to space confinement effect during the in-situ sulfurization process, which generates the interlayer-expanded and sulfur-enriched MoS_2+x nanosheets on amorphous carbon hollow spheres. This new sulfur host possesses multifarious merits including sufficient voids for loading sulfur active materials, high electronic conductivity, and fast lithium-ion diffusive pathways. In addition, additional active edge sites of MoS_2+x accompanied by the nitrogen-doped carbon species endow the sulfur host with immobilizing and catalyzing effects on the soluble polysulfide species, dramatically accelerating their conversion kinetics and re-utilization. The detailed defect-induced interface catalytic reaction mechanism is firstly proposed. As expected, the delicately-designed sulfur host exhibits an outstanding initial discharge capacity of 1, 249 mAh·g^-1 at 0.2 C and a desirable rate performance (593 mAh·g^-1 at 5.0 C), implying its great prospects in achieving superior electrochemical performances for advanced lithium sulfur batteries.