Dual Network Sponge for Compressible Lithium-Ion Batteries.

Compressible energy devices have received increasing attention with the rapid development of flexible electronics and wearable devices due to their size adaptability and functional stability. However, it is hard to simultaneously achieve satisfactory energy density and mechanical stability for electrodes. Here an open-porous dual network sponge (DNS) with two networks of highly conductive carbon nanotubes and Li+ -intercalating TiO2 -B nanowires is synthesized and employed as compressible lithium ion battery electrodes. All 1D components inside the DNS mutually penetrate with each other to form two physically distinct but functionally coupling networks, endowing DNS excellent compressibility and stability. A prototype compressible lithium-ion battery (C-LIB) is also demonstrated, in which the DNS exhibits a specific capacity of >238 mAh g-1 under static 50% strain, and further in situ measurements show that under 1000 times of cyclic strains, DNS can charge and discharge normally maintaining a high capacity of 240 mAh g-1 and exhibits robustness to fast strain rates up to 500% min-1 . The dual network structure can be extended to design high-performance compliant electrodes that are promising to serve in future compressible and deformable electronics and energy systems.

Porous-Carbon Aerogels with Tailored Sub-Nanopores for High Cycling Stability and Rate Capability Potassium-Ion Battery Anodes.

Developing advanced electrode materials for potassium-ion batteries (PIBs) is an emerging research area in recent years; so far, several strategies such as heteroatom doping into carbon, increasing interlayer spacing, or creating amorphous region in graphite have been investigated. Here, we studied the effect of sub-nanopores in a porous-carbon aerogel with a pore size distribution centered at around 0.8 nm and achieved outstanding PIB performance including long cycling stability (particularly at small current densities for prolonged charge/discharge period) and high rate capability with enhanced retentions. Mechanism studies reveal very high contribution from surface capacitive potassium (K)-ion storage (more than 90%) to the total capacity, and theoretical calculations show that 0.8 nm sub-nanopores lead to substantially low barrier for K-ion transport and storage, with ultrasmall diffusion energy and negligible lattice change. Sub-nanopore engineering, as demonstrated here, may be adopted to develop highly efficient and stable porous-carbon-based structures for applications in advanced energy storage systems and electrochemical catalysis.

Controlled Air-Etching Synthesis of Porous-Carbon Nanotube Aerogels with Ultrafast Charging at 1000 A g-1.

Supercapacitors are energy storage systems capable of fast charging and discharging, thus generating superior power density. Porous carbon with high surface area and tunable pore size represents a promising candidate to construct ultrafast supercapacitors; so far, most porous carbon-based electrodes can only be charged to a moderate current density (100-200 A g-1), also with significant capacitance loss at increasing rate. Here, it is shown that a 3D aerogel consisting of interconnected 1D porous-carbon nanotubes (PCNs) can serve as a freestanding supercapacitor electrode with excellent rate performance. As a result, the PCN aerogel electrodes achieve 1) ultrafast charging at current densities up to 1000 A g-1 (corresponding to a charge period of 16 ms), which is the highest value among other porous carbon-based supercapacitors, 2) superior cycling stability at high charging rates (88% capacitance retention after 105 cycles at 1000 A g-1). Mechanism study reveals favorable kinetics including a centralized pore size distribution at 0.8 nm which is a dominant factor to allow high-rate charging, a low and linear IR drop, and a metallic feature of 1D PCNs by theoretical calculation. The results indicate that 1D PCNs with controlled porous structures have potential applications in ultrafast energy conversion and storage.

Hyperporous Sponge Interconnected by Hierarchical Carbon Nanotubes as a High-Performance Potassium-Ion Battery Anode.

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-1 , 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.

Single Carbon Fibers with a Macroscopic-Thickness, 3D Highly Porous Carbon Nanotube Coating.

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.

MOF-Derived ZnO Nanoparticles Covered by N-Doped Carbon Layers and Hybridized on Carbon Nanotubes for Lithium-Ion Battery Anodes.

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.

Graphene Oxide Glue-Electrode for Fabrication of Vertical, Elastic, Conductive Columns.

Graphene has a planar atomic structure with high flexibility and might be used as ultrathin conductive glues or adhesion layers in electronics and other applications. Here, we show that graphene oxide (GO) sheets condensed from solution can act as a pure, thin-layer, nonpenetrating glue for fabrication of vertical architectures anchored on rigid and flexible substrates. Carbon nanotube (CNT) sponges are used as a porous template to make polymer-reinforced composite columns, to achieve both high conductivity and elastic behavior. These vertical columns are fixed on a substrate by reduced GO sheets as an electrode and exhibit reversible resistance change under large-strain compression for many cycles. Similar to the CNT gecko feet, we disclose high adhesion forces at the CNT-GO and GO-SiO2 interfaces by mechanical tests and theoretical calculation. Three-dimensional CNT, graphene, and nanowire networks with our GO glue-electrodes have potential applications as energy storage electrodes, flexible sensors, functional composites, and vertical interconnects.