The Fusion of Imidazolium‐Based Ionic Polymer and Carbon Nanotubes: One Type of New Heteroatom‐Doped Carbon Precursors for High‐Performance Lithium–Sulfur Batteries

Rational design of sulfur host materials with high electrical conductivity and strong polysulfides (PS) confinement is indispensable for high‐performance lithium–sulfur (Li–S) batteries. This study presents one type of new polymer material based on main‐chain imidazolium‐based ionic polymer (ImIP) and carbon nanotubes (CNTs); the polymer composites can serve as a precursor of CNT/NPC‐300, in which close coverage and seamless junction of CNTs by N‐doped porous carbon (NPC) form a 3D conductive network. CNT/NPC‐300 inherits and strengthens the advantages of both high electrical conductivity from CNTs and strong PS entrapping ability from NPC. Benefiting from the improved attributes, the CNT/NPC‐300‐57S electrode shows much higher reversible capacity, rate capability, and cycling stability than NPC‐57S and CNTs‐56S. The initial discharge capacity of 1065 mA h g^?1 is achieved at 0.5 C with the capacity retention of 817 mA h g^?1 over 300 cycles. Importantly, when counter bromide anion in the composite of CNTs and ImIP is metathesized to bis(trifluoromethane sulfonimide), heteroatom sulfur is cooperatively incorporated into the carbon hosts, and the surface area is increased with the promotion of micropore formation, thus further improving electrochemical performance. This provides a new method for optimizing porous properties and dopant components of the cathode materials in Li–S batteries.     

Properties of Carbon Nanotube Fibers Spun from DNA‐Stabilized Dispersions

The fabrication of single‐walled carbon nanotube (CNT) fibers containing (salmon) DNA has been demonstrated. The DNA material has been found to be adequate for dispersing relatively large concentrations (up to 1 % by weight) of carbon nanotubes. These dispersions are better suited for fiber spinning than previously studied dispersions based on conventional surfactants, such as sodium dodecyl sulfate (SDS). The DNA‐containing fibers were less conductive than the fibers based on SDS, but they were significantly stronger. Considerably increased conductivity was obtained by thermally annealing the CNT/DNA fibers, a process accompanied by a loss in mechanical strength. Smaller improvements in conductivity could be introduced by annealing the carbon nanotubes before fiber production, with no alteration of the fiber mechanical properties. Those CNT/DNA fibers that were mechanically strong and conductive also exhibited good electrochemical behavior and useful capacitance values (up to 7.2 F g^–1).     

Macroscopic and Mechanically Robust Hollow Carbon Spheres with Superior Oil Adsorption and Light‐to‐Heat Evaporation Properties

Hollow carbon spheres (HCSs) represent a special class of functional materials, to which intense interest has been paid in the fields of materials science and chemistry. A major problem with these materials is the lack of sufficient particle engineering and mechanical strength for practical applications and the difficulty of up‐scaling. Herein, we report a general, template‐free, phase‐separation approach, in which the liquid–liquid phase‐inversion process and a gas‐foaming process are coupled for the first time, for fast and continuous processing of uniform HCSs. The obtained HCSs have particle sizes on the millimeter scale, and a hierarchical structure with an interpenetrating, open‐porous, carbon shell and huge external voids, therefore permitting rapid transport of molecules into, throughout, and out of the hollow structure. By evenly dispersing the CNTs in the precursor solution, CNT‐reinforced HCSs can be achieved with significantly enhanced mechanical strength, hydrophobicity, and electronic and thermal properties. The resulting CNT‐reinforced HCSs offer a viable route to remove the engine oil from water in a fixed‐bed system. Moreover, these floatable HCSs can receive and convert sunlight to heat at the water–air interface, resulting in a great enhancement in solar evaporation rate compared to conventional bulk heating schemes.     

Ultrahigh Electrical Resistance of Poly(cyclohexyl methacrylate)/Carbon Nanotube Composites Prepared Using Surface‐Initiated Polymerization

Multiwalled carbon nanotubes on which poly(cyclohexyl methacrylate)s are densely grafted (PCHMA‐CNTs), are synthesized using a modified surface‐initiated atom transfer radical polymerization technique. The electrical resistance of PCHMA‐CNT is systematically characterized under direct current (DC) and alternating current and compared to that of conventional nanocomposites prepared by blending PCHMA with the CNT (PCHMA/CNT). At a comparable volume fraction of CNT, DC volume resistivity of PCHMA‐CNT is 14 orders of magnitude higher than that of PCHMA/CNT. This is because the grafted polymer with a combination of the high molecular weight and the high grafting density isolates individual CNTs at a long distance in the PCHMA‐CNT system. In addition, impedance analysis reveals that the highly insulated PCHMA‐CNT has the same electrical nature as neat PCHMA, i.e., it is a dielectric. Furthermore, dynamic mechanical analysis shows PCHMA‐CNT has a good mechanical properties as well as ultrahigh electrical resistance.     

Mechanical Properties of Functionalized Single‐Walled Carbon‐Nanotube/Poly(vinyl alcohol) Nanocomposites

Nanocomposites based on semi‐crystalline poly(vinyl alcohol) (PVA) and well‐dispersed chemically functionalized single‐walled carbon nanotubes are combined through simple mixing. The interaction between the nanotubes and the polymer matrix is studied using optical and thermal methods. Significant enhancement of the mechanical properties is obtained for the functionalized‐nanotube‐based composites. These results imply that promoting nanotube dispersion and strong interfacial bonding through adequate functionalization of nanotubes improves the load transfer from the matrix to the reinforcing phase.     

Flexible Multifunctionalized Carbon Nanotubes‐Based Hybrid Nanowires

In this work, flexible multifunctionalized carbon nanotube (CNT)‐based hybrid nanowires are synthesized through surface modification processes. The good dispersability of the hybrid nanowire in polar solvents facilitates directly making fine patterns with a minimum width of 40 μm for applications of flexible and stretchable circuits (FSCs). The hybrid nanowire possesses a flexible and highly conductive structure which demonstrates stable electro‐mechanical properties on polydimethylsiloxane (PDMS) substrates under large structural deformation. FSCs fabricated from the hybrid nanowires show a constant resistance of 0.096 Ω □^?1 (equivalent of a resistivity 0.96 Ω μm) under repeated bending cycles. The FSCs also have a low and stable sheet resistance of 0.4 Ω □^?1 for strains up to 30%, which is almost four orders of magnitude lower than that of pure CNT samples (1316 Ω □^?1). Further improved stretchability and electro‐mechanical properties (0.1 Ω □^?1, at the strain of 100%) are achieved with a prestrain PDMS substrate. Repeated deformation tests demonstrate the high reliability of FSCs. The observed stable and reliable electro‐mechanical performance of FSCs suggests the potential use of the material in wearable and portable electronics.     

A Versatile,Molecular Engineering Approach to Simultaneously Enhanced,Multifunctional Carbon‐Nanotube– Polymer Composites

Single‐walled carbon nanotubes (SWNTs) are recognized as the ultimate carbon fibers for high‐performance, multifunctional composites. The remarkable multifunctional properties of pristine SWNTs have proven, however, difficult to harness simultaneously in polymer composites, a problem that arises largely because of the smooth surface of the carbon nanotubes (i.e., sidewalls), which is incompatible with most solvents and polymers, and leads to a poor dispersion of SWNTs in polymer matrices, and weak SWNT–polymer adhesion. Although covalently functionalized carbon nanotubes are excellent reinforcements for mechanically strong composites, they are usually less attractive fillers for multifunctional composites, because the covalent functionalization of nanotube sidewalls can considerably alter, or even destroy, the nanotubes' desirable intrinsic properties. We report for the first time that the molecular engineering of the interface between non‐covalently functionalized SWNTs and the surrounding polymer matrix is crucial for achieving the dramatic and simultaneous enhancement in mechanical and electrical properties of SWNT–polymer composites. We demonstrate that the molecularly designed interface of SWNT–matrix polymer leads to multifunctional SWNT–polymer composite films stronger than pure aluminum, but with only half the density of aluminum, while concurrently providing electroconductivity and room‐temperature solution processability.     

High‐Temperature BiScO3‐PbTiO3 Piezoelectric Vibration Energy Harvester

Conventionally, effective mechanical vibration energy harvesting is based on (Pb,Zr)TiO₃ (PZT) ceramics, poly(vinylidene fluoride) (PVDF) polymers or PVDF/PZT or other piezoelectric composite materials, and their working temperature is normally limited to room temperature (R‐T) or below 150 °C. Here, bismuth scandium lead titanate (BiScO₃‐PbTiO₃, abbreviated as BSPT) ceramic is reported which has a high Curie temperature point around 450 °C and its application for high‐temperature (H‐T) vibration energy harvesting. Experimental results show that it exhibits an excellent H‐T piezoelectricity, converting mechanical vibration energy into electric power effectively in a wide temperature range from R‐T till 250 °C. This research shows the BSPT piezoelectric energy harvester having the potential application for self‐power source of wireless sensor network system in high temperature circumstance.     

Wide Range Control of Microstructure and Mechanical Properties of Carbon Nanotube Forests: A Comparison Between Fixed and Floating Catalyst CVD Techniques

Vertically aligned carbon nanotube (CNT) forests may be used as miniature springs, compliant thermal interfaces, and shock absorbers, and for these and other applications it is vital to understand how to engineer their mechanical properties. Herein is investigated how the diameter and packing density within CNT forests govern their deformation behavior, structural stiffness, and elastic energy absorption properties. The mechanical behavior of low‐density CNT forests grown by fixed catalyst CVD methods and high‐density CNT forests grown by a floating catalyst CVD method are studied by in situ SEM compression testing and tribometer measurements of force‐displacement relationships. Low‐density and small‐diameter CNT columns (fixed catalyst) exhibit large plastic deformation and can be pre‐deformed to act as springs within a specified elastic range, whereas high‐density and large‐diameter CNT columns (floating catalyst) exhibit significant elastic recovery after deformation. In this work the energy absorption capacity of CNT forests is tuned over three orders of magnitude and it is shown that CNT forest density can be tuned over a range of conventional foam materials, but corresponding stiffness is ～10× higher. It is proposed that the elastic behavior of CNT forests is analogous to open‐cell foams and a simple model is presented. It is also shown that this model can be useful as a first‐order design tool to establish design guidelines for the mechanical properties of CNT forests and selection of the appropriate synthesis method.     

Mechanical Characterization of Amyloid Fibrils Using Coarse‐Grained Normal Mode Analysis

Recent experimental studies have shown that amyloid fibril formed by aggregation of β peptide exhibits excellent mechanical properties comparable to other protein materials such as actin filaments and microtubules. These excellent mechanical properties of amyloid fibrils are related to their functional role in disease expression. This indicates the necessity of understanding how an amyloid fibril achieves the remarkable mechanical properties through self‐aggregation with structural hierarchy. However, the structure‐property–function relationship still remains elusive. In this work, the mechanical properties of human islet amyloid polypeptide (hIAPP) are studied with respect to its structural hierarchies and structural shapes by coarse‐grained normal mode analysis. The simulation shows that hIAPP fibril can achieve the excellent bending rigidity via specific aggregation patterns such as antiparallel stacking of β peptides. Moreover, the length‐dependent mechanical properties of amyloids are found. This length‐dependent property has been elucidated from a Timoshenko beam model that takes into account the shear effect on the bending of amyloids. In summary, the study sheds light on the importance of not only the molecular architecture, which encodes the mechanical properties of the fibril, but also the shear effect on the mechanical (bending) behavior of the fibril.     

High Mechanical Performance Composite Conductor: Multi‐Walled Carbon Nanotube Sheet/Bismaleimide Nanocomposites

Multi‐walled carbon nanotube (MWNT)‐sheet‐reinforced bismaleimide (BMI) resin nanocomposites with high concentrations (～60 wt%) of aligned MWNTs are successfully fabricated. Applying simple mechanical stretching and prepregging (pre‐resin impregnation) processes on initially randomly dispersed, commercially available sheets of millimeter‐long MWNTs leads to substantial alignment enhancement, good dispersion, and high packing density of nanotubes in the resultant nanocomposites. The tensile strength and Young's modulus of the nanocomposites reaches 2 088 MPa and 169 GPa, respectively, which are very high experimental results and comparable to the state‐of‐the‐art unidirectional IM7 carbon‐fiber‐reinforced composites for high‐performance structural applications. The nanocomposites demonstrate unprecedentedly high electrical conductivity of 5 500 S cm^?1 along the alignment direction. Such unique integration of high mechanical properties and electrical conductance opens the door for developing polymeric composite conductors and eventually structural composites with multifunctionalities. New fracture morphology and failure modes due to self‐assembly and spreading of MWNT bundles are also observed.     

Ordered Mesoporous Carbon/Fused Silica Composites

A series of novel, dense, and interesting ordered mesoporous carbon (OMC)/fused silica composites with different carbon contents has been prepared by a controllable but simple sol‐gel method followed by hot‐pressing. In the as‐sintered OMC/fused silica composites the carbon particles still exist in the form of perfectly ordered carbon nanowires. Conductivity measurements on the composites indicate that these novel composites are electrically conductive and have a typical percolation threshold of 3.5–5 vol% OMC. The electromagnetic interference (EMI) shielding efficiency (SE) of an OMC/fused silica composite containing 10 vol% OMC is as high as 40 dB in the X band which is higher than that of a carbon nanotube (CNT)/ fused silica composite with the same carbon content (～30 dB). This indicates that these conductive OMC/fused silica composites are very suitable for an application as EMI shielding materials. Upon increasing the volume content of OMC in the composite the overall contribution as well as the increase rate of the microwave absorption are larger than those of the microwave reflection, which suggest that OMC/fused silica composites may also be promising electromagnetic (EM) wave absorbing materials. Based on the promising properties of these composites this work will hopefully lead to the development of new low‐cost and highly efficient EMI shielding or EM wave absorbing materials.     

Yellow‐Colored Electro‐Optic Crystals as Intense Terahertz Wave Sources

This study presents newly developed yellow‐colored organic electro‐optic crystals to provide high terahertz (THz) wave generation efficiency. Compared with currently existing red‐ or orange‐colored electro‐optic crystals, which are used for most benchmark organic THz sources, yellow‐colored crystals have additional superior advantages for THz wave generation, e.g., higher transparency in the visible wavelength range with accompanying different phase‐matching possibilities. The new yellow‐colored crystals consist of a highly nonlinear optical 4‐(4‐hydroxystyryl)‐1‐methylpyridinium (OHP) cation, with a relatively short wavelength of maximal absorption at 390 nm in solution, and various halogen‐substituted benzenesulfonate anions, with strong secondary‐bonding ability. OHP 4‐chlorobenzenesulfonate (OHP‐CBS) crystals exhibit large off‐resonant macroscopic optical nonlinearity and high transparency, with a cut‐off wavelength for solid‐state absorption near 490 nm. OHP‐CBS crystals provide excellent THz wave generation characteristics based on optical rectification. A 0.53 mm thick OHP‐CBS crystal delivers ≈27 times higher optical‐to‐THz conversion efficiency and a much broader spectrum bandwidth compared with the standard 1.0 mm thick ZnTe at 1300 nm pumping. Particularly, compared with a benchmark organic quinolinium crystal with a similar thickness of 0.55 mm, OHP‐CBS crystals exhibit 1.7 times higher optical‐to‐THz conversion efficiency, and show a significantly different THz spectral shape.     

Transparent Nacre‐like Composites Toughened through Mineral Bridges

Bulk materials with remarkable mechanical properties have been developed by incorporating design principles of biological nacre into synthetic composites. However, this potential has not yet been fully leveraged for the fabrication of tough and strong materials that are also optically transparent. In this work, a manufacturing route that enables the formation of nacre‐like mineral bridges in a bioinspired composite consisting of glass platelets infiltrated with an index‐matching polymer matrix is developed. By varying the pressure applied during compaction of the glass platelets, composites with tunable levels of mineral bridges and platelet interconnectivity can be easily fabricated. The effect of platelet interconnectivity on the mechanical strength and fracture behavior of the bioinspired composites is investigated by performing state‐of‐the‐art fracture experiments combined with in situ electron microscopy. The results show that the formation of interconnections between platelets leads to bulk transparent materials with an unprecedented combination of strength and fracture toughness. This unusual set of properties can potentially fulfill currently unmet demands in electronic displays and related technologies.     

Energy‐Dissipative Matrices Enable Synergistic Toughening in Fiber Reinforced Soft Composites

Tough hydrogels have shown strong potential as structural biomaterials. These hydrogels alone, however, possess limited mechanical properties (such as low modulus) when compared to some load‐bearing tissues, e.g., ligaments and tendons. Developing both strong and tough soft materials is still a challenge. To overcome this obstacle, a new material design strategy has been recently introduced by combining tough hydrogels with woven fiber fabric to create fiber reinforced soft composites (FRSCs). The new FRSCs exhibit extremely high toughness and tensile properties, far superior to those of the neat components, indicating a synergistic effect. Here, focus is on understanding the role of energy dissipation of the soft matrix in the synergistic toughening of FRSCs. By selecting a range of soft matrix materials, from tough hydrogels to weak hydrogels and even a commercially available elastomer, the toughness of the matrix is determined to play a critical role in achieving extremely tough FRSCs. This work provides a good guide toward the universal design of soft composites with extraordinary fracture resistance capacity.     

Carbon‐Nanotube‐Templated,Sputter‐Deposited,Flexible Superconducting NbN Nanowire Yarns

Flexible superconducting yarns consisting of sputter‐deposited NbN nanowires on highly aligned carbon nanotube (CNT) array sheets are reported. In the microscopic view, the NbN nanowires are formed on top of individual CNT fibrils, and the superconductivity property of the twist‐spun NbN–CNT yarn system is comparable to that of a typical NbN thin film on a normal solid substrate. Because of its intrinsic porosity, the system exhibits superior mechanical flexibility with a small bending radius. It also remains a superconducting state even when subjected to severe mechanical deformations, primarily due to the proximity superconductivity through carbon nanotube bundles. The results demonstrate the possibility of fabricating flexible superconducting yarns in a conventional thin‐film deposition process, using ultraflexible free‐standing CNT sheets as a template. In addition, preliminary tests on reducing the normal‐state resistance toward superconducting cable applications are presented.     

One‐Pot Synthesis of Antimony‐Embedded Silicon Oxycarbide Materials for High‐Performance Sodium‐Ion Batteries

Sodium‐ion batteries have recently attracted intensive attention due to their natural abundance and low cost. Antimony is a desirable candidate for an anode material for sodium‐ion batteries due to its high theoretical capacity (660 mA h g^?1). However, the utilization of alloy‐based anodes is still limited by their inherent huge volume changes and sluggish kinetics. The Sb‐embedded silicon oxycarbide (SiOC) composites are simply synthesized via a one‐pot pyrolysis process at 900 °C without any additives or surfactants, taking advantage of the superior self‐dispersion properties of antimony acetate powders in silicone oil. The structural and morphological characterizations confirm that Sb nanoparticles are homogeneously embedded into the amorphous SiOC matrix. The composite materials exhibit an initial desodiation capacity of around 510 mA h g^?1 and maintained an excellent capacity retention above 97% after 250 cycles. The rate capability test reveals that the composites deliver capacity greater than 453 mA h g^?1, even at the high current density of 20 C rate, owing to the free‐carbon domain of SiOC material. The electrochemical and postmortem analyses confirm that the SiOC matrix with a uniform distribution of Sb nanoparticles provides the mechanical strength without degradation in conductive characteristics, suppressing the agglomeration of Sb particles during the electrochemical reaction.     

Facile Preparation of High‐Content N‐Doped CNT Microspheres for High‐Performance Lithium Storage

Herein, high‐content N‐doped carbon nanotube (CNT) microspheres (HNCMs) are successfully synthesized through simple spray drying and one‐step pyrolysis. HNCM possesses a hierarchically porous architecture and high‐content N‐doping. In particular, HNCM800 (HNCM pyrolyzed at 800 °C) shows high nitrogen content of 12.43 at%. The porous structure derived from well‐interconnected CNTs not only offers a highly conductive network and blocks diffusion of soluble lithium polysulfides (LiPSs) in physical adsorption, but also allows sufficient sulfur infiltration. The incorporation of N‐rich CNTs provides strong chemical immobilization for LiPSs. As a sulfur host for lithium–sulfur batteries, good rate capability and high cycling stability is achieved for HNCM/S cathodes. Particularly, the HNCM800/S cathode delivers a high capacity of 804 mA h g^?1 at 0.5 C after 1000 cycles corresponding to low fading rate (FR) of only 0.011% per cycle. Remarkably, the cathode with high sulfur loading of 6 mg cm^?2 still maintains high cyclic stability (capacity of 555 mA h g^?1 after 1000 cycles, FR 0.038%). Additionally, CNT/Co₃O₄ microspheres are obtained by the oxidation of CNTs/Co in the air. The as‐prepared CNT/Co₃O₄ microspheres are employed as an anode for lithium‐ion batteries and present excellent cycling performance.     

Highly Elastic,Transparent, and Conductive 3D‐Printed Ionic Composite Hydrogels

Despite extensive progress to engineer hydrogels for a broad range of technologies, practical applications have remained elusive due to their (until recently) poor mechanical properties and lack of fabrication approaches, which constrain active structures to simple geometries. This study demonstrates a family of ionic composite hydrogels with excellent mechanical properties that can be rapidly 3D‐printed at high resolution using commercial stereolithography technology. The new material design leverages the dynamic and reversible nature of ionic interactions present in the system with the reinforcement ability of nanoparticles. The composite hydrogels combine within a single platform tunable stiffness, toughness, extensibility, and resiliency behavior not reported previously in other engineered hydrogels. In addition to their excellent mechanical performance, the ionic composites exhibit fast gelling under near‐UV exposure, remarkable conductivity, and fast osmotically driven actuation. The design of such ionic composites, which combine a range of tunable properties and can be readily 3D‐printed into complex architectures, provides opportunities for a variety of practical applications such as artificial tissue, soft actuators, compliant conductors, and sensors for soft robotics.     

Self‐Assembly of Mechanoplasmonic Bacterial Cellulose–Metal Nanoparticle Composites

Nanocomposites of metal nanoparticles (NPs) and bacterial nanocellulose (BC) enable fabrication of soft and biocompatible materials for optical, catalytic, electronic, and biomedical applications. Current BC–NP nanocomposites are typically prepared by in situ synthesis of the NPs or electrostatic adsorption of surface functionalized NPs, which limits possibilities to control and tune NP size, shape, concentration, and surface chemistry and influences the properties and performance of the materials. Here a self‐assembly strategy is described for fabrication of complex and well‐defined BC–NP composites using colloidal gold and silver NPs of different sizes, shapes, and concentrations. The self‐assembly process results in nanocomposites with distinct biophysical and optical properties. In addition to antibacterial materials and materials with excellent senor performance, materials with unique mechanoplasmonic properties are developed. The homogenous incorporation of plasmonic gold NPs in the BC enables extensive modulation of the optical properties by mechanical stimuli. Compression gives rise to near‐field coupling between adsorbed NPs, resulting in tunable spectral variations and enhanced broadband absorption that amplify both nonlinear optical and thermoplasmonic effects and enables novel biosensing strategies.