Robust anchoring of high‐capacity nanocrystals (NCs) on porous conductive substrates is of paramount importance but it is challenging for highly efficient energy storage to prevent the weak interfacial interactions, inevitable aggregation, and sluggish charge transfer, due to the technical hurdles of constructing heterostructures with firm electron/ion bridging. Herein, a facile and high‐efficiency liquid‐phase laser manufacturing strategy to guarantee the covalent bonding of ultrafine NCs on conductive substrates by predesigning metastable supranano (<10 nm) particles is proposed. The manufacturing of supranano SnO2 (≈3.4 nm) is demonstrated to tightly anchor on mesoporous walls of graphene with high loading (≈81.3%) and homogenous dispersion. Such a optimized heterostructure with unimpeded electron/ion transfer delivers extraordinary long‐term cycling stability (1132 mAh g–1 at 1.0 A g–1 after 1250 cycles) and impressive rate capability (275 mAh g–1 at 30.0 A g–1) as the anode for Li‐storage, which are some of the highest values among the reported SnO2‐based anodes. The study provides an important avenue for addressing the interfacial bridging in‐between heterostructures via creating active metastable supranano particles for intriguing electrochemical applications or even beyond, based on laser‐matter interactions.

Lithium Storage In article number 2101059, Liang Li, Hongqiang Wang, and co-workers construct firm interfacial bridging in-between the heterostructure of SnO2 and graphene via laser manufacturing of metastable supranano SnOx particles. This optimized heterostructure enables rapid electron/ion transfer and impregnable nanoparticle confinement even in cases of heavy loading. The resulting electrode delivers extraordinary long-term cycling stability and rate capability for Li storage.

Room-temperature sodium-sulfur (RT-Na/S) batteries are an important class of rechargeable batteries with a high theoretical capacity of 1675 mAh g-1 and energy density up to 1276 Wh kg-1. Together with the abundant and cheap sodium and sulfur, RT-Na/S batteries are recognized as one of the attractive next-generation high-energy-density devices for large-scale energy storage. However, similar to the working principle in lithium-sulfur batteries, RT-Na/S batteries suffer from some essential problems such as the poor conductivity of elemental sulfur, the large volume change during charge-discharge cycling and the serious shuttle effect caused by sodium polysulfides dissolution. Moreover, the shuttle effect and volume variation seem more pronounced in RT-Na/S batteries, which further deteriorates their performances and seriously hinders the progress towards practical application. Recent years have witnessed a fast growth of designing porous carbons especially hollow carbon spheres (HCSs) as sulfur host to address these problems, due to their unique structural features such as special shape, large void space, permeable shell and facile functionalization. This review summarizes the recent progress of HCSs-based materials as the sulfur hosts in RT-Na/S batteries. Beginning with a brief introduction to RT-Na/S batteries, carbon hosts and design strategies for preparing HCSs, emphasis is then placed on manipulating the pore structure, heteroatom doping and metal species decoration with the aim to alleviate the "shuttle effect" and thus to improve the performance. Finally, perspectives on current challenge and future directions are also discussed.

Potassium-ion batteries (PIBs) hold great promise as alternatives to lithium ion batteries in post-lithium age, while face challenges of slow reaction kinetics induced by the inherent characteristics of large-size K+. We herein show that creating sufficient exposed edges in MoS2 via constructing ordered mesoporous architecture greatly favors for improved kinetics as well as increased reactive sites for K storage. The engineered MoS2 with edge-enriched planes (EE-MoS2) is featured by three-dimensional bicontinuous frameworks with ordered mesopores of ~ 5.0 nm surrounded by thin wall of ~9.0 nm. Importantly, EE-MoS2 permits exposure of enormous edge planes at pore walls, renders its intrinsic layer spacing more accessible for K+ and accelerates conversion kinetics, thus realizing enhanced capacity and high rate capability. Impressively, EE-MoS2 displays a high reversible charge capacity of 506 mAh·g−1 at 0.05 A·g−1, superior cycling capacities of 321 mAh·g−1 at 1.0 A·g−1 after 200 cycles and a capacity of 250 mAh·g−1 at 2.0 A·g−1, outperforming edge-deficient MoS2 with nonporous bulk structure. This work enlightens the nanoarchitecture design with abundant edges for improving electrochemical properties and provides a paradigm for exploring high-performance PIBs.

Rational manipulation of the carbon framework from the microporous to nonporous via a molecular design approach is interesting but challenging. Herein, we report a versatile strategy for transforming the microporous carbon framework to the low porous one by an elaborate molecular crosslinker design in the polystyrene (PS) precursor. Direct coupling of benzene rings in PS via Scholl reaction yields hypercrosslinked PS-derived carbon with low porous framework, while insertion of methylene crosslinker into PS via a solvent knitting strategy leads to microporous carbon framework. The results show that methylene crosslinker functions as molecular-scale soft templates for facilitating micropores, whereas direct linking PS chains promotes aromatization and mitigates micropore formation during the pyrolysis. The distinct carbon frameworks derived from similar precursor and pyrolysis condition provide an intriguing platform for structure-property relationship study, as preliminarily exemplified by the application in Na ion storage. The low-porosity carbon shows higher initial Coulombic efficiency and superior capacity thanks to its low surface area and enhanced Na insertion into pseudo-graphitic microcrystal structure. The present protocol opens up new avenues towards flexible carbon framework porosity manipulation at molecular level and would trigger further efforts for low-porosity carbons in energy storage.

The incorporation of functional building blocks to construct functionalized and highly porous covalent triazine frameworks (CTFs) is essential to the emerging adsorptive-involved field. Herein, a series of amide functionalized CTFs (CTF-PO71) have been synthesized using a bottom-up strategy in which pigment PO71 with an amide group is employed as a monomer under ionothermal conditions with ZnCl2 as the solvent and catalyst. The pore structure can be controlled by the amount of ZnCl2 to monomer ratio. Benefitting from the highly porous structure and amide functionalities, CTF-PO71, as a sulfur cathode host, simultaneously demonstrates physical confinement and chemical anchoring of sulfur species, thus leading to superior capacity, cycling stability, and rate capability in comparison to unfunctionalized CTF. Meanwhile, as an adsorbent of organic dye molecules, CTF-PO71 was demonstrated to exhibit strong chemical interactions with dye molecules, facilitating adsorption kinetics and thereby promoting the adsorption rate and capacity. Furthermore, the dynamic adsorption experiments of organic dyes from solutions showed selectivity/priority of CTF-PO71s for specific dye molecules.