Recently, commercial graphite and other carbon-based materials have shown promising properties as the anode for potassium-ion batteries. A fundamental problem related to those carbon electrodes, significant volume expansion, and structural instability/collapsing caused by cyclic K-ion intercalation, remains unsolved and severely limits further development and applications of K-ion batteries. Here, a multiwalled hierarchical carbon nanotube (HCNT) is reported to address the issue, and a reversible specific capacity of 232 mAh g , excellent rate capability, and cycling stability for 500 cycles are achieved. The key structure of the HCNTs consists of an inner CNT with dense-stacked graphitic walls and a loose-stacked outer CNT with more disordered walls, and individual HCNTs are further interconnected into a hyperporous bulk sponge with huge macropore volume, high conductivity, and tunable modulus. It is discovered that the inner dense-CNT serves as a robust skeleton, and collectively, the outer loose-CNT is beneficial for K-ion accommodation; meanwhile the hyperporous sponge facilitates reaction kinetics and offers stable surface capacitive behavior. The hierarchical carbon nanotube structure has great potential in developing high-performance and stable-structure electrodes for next generation K and other metal-ion batteries.

Metal‐organic frameworks (MOFs) hybridized with a conductive matrix could potentially serve as a sulfur host for lithium‐sulfur (Li‐S) battery electrodes; so far most of the previously studied hybrid structures are in the powder form or thin compact films. This study reports 3D porous MOF@carbon nanotube (CNT) networks by grafting MOFs with tailored particle size uniformly throughout a CNT sponge skeleton. Growing larger‐size MOF particles to entrap the conductive CNT network yields a mutually embedded structure with high stability, and after sulfur encapsulation, it shows an initial discharge capacity of ≈1380 mA h g−1 (at 0.1 C) and excellent cycling stability with a very low fading rate. Furthermore, owing to the 3D porous network that is suitable for enhanced sulfur loading, a remarkable areal capacity of ≈11 mA h cm−2 (at 0.1 C) is obtained, which is much higher than other MOF‐based hybrid electrodes. The mutually embedded MOF@CNTs with simultaneously high specific capacity, areal capacity, and cycling stability represent an advanced candidate for developing high‐performance Li‐S batteries and other energy storage systems.

Carbon fiber (CF) grafted with a layer of carbon nanotubes (CNTs) plays an important role in composite materials and other fields; to date, the applications of CNTs@CF multiscale fibers are severely hindered by the limited amount of CNTs grafted on individual CFs and the weak interfacial binding force. Here, monolithic CNTs@CF fibers consisting of a 3D highly porous CNT sponge layer with macroscopic-thickness (up to several millimeters), which is directly grown on a single CF, are fabricated. Mechanical tests reveal high sponge-CF interfacial strength owing to the presence of a thin transitional layer, which completely inhibits the CF slippage from the matrix upon fracture in CNTs@CF fiber-epoxy composites. The porous conductive CNTs@CF hybrid fibers also act as a template for introducing active materials (pseudopolymers and oxides), and a solid-state fiber-shaped supercapacitor and a fiber-type lithium-ion battery with high performances are demonstrated. These CNTs@CF fibers with macroscopic CNT layer thickness have many potential applications in areas such as hierarchically reinforced composites and flexible energy-storage textiles.

Metal-organic frameworks (MOFs) have many promising applications in energy and environmental areas such as gas separation, catalysis, supercapacitors, and batteries; the key toward those applications is controlled pyrolysis which can tailor the porous structure, improve electrical conductivity, and expose metal ions in MOFs. Here, we present a systematic study on the structural evolution of zeolitic imidazolate frameworks hybridized on carbon nanotubes (CNTs) during the carbonization process. We show that a number of typical products can be obtained, depending on the annealing time, including (1) CNTs wrapped by relatively thick carbon layers, (2) CNTs grafted by ZnO nanoparticles which are covered by thin nitrogen-doped carbon layers, and (3) CNTs grafted by aggregated ZnO nanoparticles. We also investigated the electrochemical properties of those hybrid structures as freestanding membrane electrodes for lithium ion batteries, and the second one (CNT-supported ZnO covered by N-doped carbon) shows the best performance with a high specific capacity (850 mA h/g at a current density of 100 mA/g) and excellent cycling stability. Our results indicate that tailoring and optimizing the MOF-CNT hybrid structure is essential for developing high-performance energy storage systems.

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