High performance supercapacitors deploying cube-templated tracheid cavities of wood-derived carbon.

Wood-derived carbon, with its strong tracheid array structure, is an ideal material for use as a self-supporting electrode in supercapacitors. By leveraging the inherent through pore structure and surface affinity found in wood tracheids, we successfully engineered a highly spatially efficient cube-templated porous carbon framework inside carbonized wood tracheid cavities through precise control over precursor crystallization temperatures. This innovative cubic channel architecture effectively maximizes up to (79 ± 1)% of the cavity volume in wood-derived carbon while demonstrating exceptional hydrophilicity and high conductivity properties, facilitating the development of supercapacitors with enhanced areal/volumetric capacitances (2.65F cm-2/53.0F cm-3 at 5.0 mA cm-2) as well as superior areal/volumetric energy densities (0.37 mWh cm-2/7.36 mWh cm-3 at 2.5 mW cm-2). The fabrication of these cube-templated channels with high cube filling content is not only simple and precisely controllable, but also environmentally friendly. The proposed method eliminates the conventional acid-base treatment process for pore formation, facilitating the rapid development and practical implementation of thick electrodes with superior performance in supercapacitors. Moreover, it offers a universal research approach for the commercialization of wood-derived thick electrodes.

Water-induced strong isotropic MXene-bridged graphene sheets for electrochemical energy storage.

Graphene and two-dimensional transition metal carbides and/or nitrides (MXenes) are important materials for making flexible energy storage devices because of their electrical and mechanical properties. It remains a challenge to assemble nanoplatelets of these materials at room temperature into in-plane isotropic, free-standing sheets. Using nanoconfined water-induced basal-plane alignment and covalent and π-π interplatelet bridging, we fabricated Ti3C2Tx MXene-bridged graphene sheets at room temperature with isotropic in-plane tensile strength of 1.87 gigapascals and moduli of 98.7 gigapascals. The in-plane room temperature electrical conductivity reached 1423 siemens per centimeter, and volumetric specific capacity reached 828 coulombs per cubic centimeter. This nanoconfined water-induced alignment likely provides an important approach for making other aligned macroscopic assemblies of two-dimensional nanoplatelets.

Selaginelladensiciliata (subg. Heterostachys, Selaginellaceae), a new spikemoss species from China based on morphological and molecular data.

A new species of spikemoss, Selaginelladensiciliata in S.subg.Heterostachyssect.Tetragonostachyae, China, is described from southeastern Xizang, based on morphological and molecular phylogenetic data. Morphologically, S.densiciliata is similar to S.repanda, S.subvaginata and S.vaginata, but the new species can be easily distinguished from them by having sterile leaves margins densely ciliate, symmetrical axillary leaves oblong ovate to ovate-triangular, and ovate dorsal leaves obviously carinate. Molecular phylogenetic analysis resolves S.densiciliata as sister to the clade comprised with S.vaginata and S.xipholepis, which confirms the recognition of the new species.

Transcriptome-Based Study on the Phylogeny and Hybridization of Marattialean Ferns (Marattiaceae).

Marattiaceae is a phylogenetically isolated family of tropical eusporangiate ferns including six genera with more than one-hundred species. In Marattiaceae, monophyly of genera has been well-supported phylogenetically. However, the phylogenetic relationships among them were elusive and controversial. Here, a dataset of 26 transcriptomes (including 11 newly generated) were used to assess single-copy nuclear genes and to obtain the organelle gene sequences. Through phylotranscriptomic analysis, the phylogeny and hybridization events of Marattiaceae were explored and a robust phylogenomic framework for the evolution of Marattiaceae was provided. Using both concatenation- and coalescent-based phylogenies, the gene-tree discordance, incomplete lineage sorting (ILS) simulations, and network inference were examined. Except the low support with mitochondrial genes of Marattiaceae, nuclear genes and chloroplast genes strongly supported a sister relationship between Marattiaceae and leptosporangiate ferns. At the genus level, all phylogenetic analysis based on nuclear genes datasets recovered five genera in Marattiaceae as monophyletic with strong support. Danaea and Ptisana were the first two diverged clades in turn. Christensenia was a sister clade to the clade Marattia + Angiopteris s.l. In Angiopteris s.l., three clades (Angiopteris s.s., the Archangiopteris group, and An. sparsisora) were well identified with maximum support. The Archangiopteris group was derived from Angiopteris s.s. at ca. 18 Ma. The putative hybrid species An. sparsisora between Angiopteris s.s. and the Archangiopteris group was verified by the species network analyses and the maternal plastid genes. This study will improve our understanding for using the phylotranscriptomic method to explore phylogeny and investigate hybridization events for difficult taxa in ferns.

Recent Advances in Carbon Nanotube-Based Energy Harvesting Technologies.

There has been enormous interest in technologies that generate electricity from ambient energy such as solar, thermal, and mechanical energy, due to their potential for providing sustainable solutions to the energy crisis. One driving force behind the search for new energy-harvesting technologies is the desire to power sensor networks and portable devices without batteries, such as self-powered wearable electronics, human health monitoring systems, and implantable wireless sensors. Various energy harvesting technologies have been demonstrated in recent years. Among them, electrochemical, hydroelectric, triboelectric, piezoelectric, and thermoelectric nanogenerators have been extensively studied because of their special physical properties, ease of application, and sometimes high obtainable efficiency. Multifunctional carbon nanotubes (CNTs) have attracted much interest in energy harvesting because of their exceptionally high gravimetric power outputs and recently obtained high energy conversion efficiencies. Further development of this field, however, still requires an in-depth understanding of harvesting mechanisms and boosting of the electrical outputs for wider applications. Here, various CNT-based energy harvesting technologies are comprehensively reviewed, focusing on working principles, typical examples, and future improvements. The last section discusses the existing challenges and future directions of CNT-based energy harvesters.

Morphology modulation of artificial muscles by thermodynamic-twist coupling.

Human muscles can grow and change their length with body development; therefore, artificial muscles that modulate their morphology according to changing needs are needed. In this paper, we report a strategy to transform an artificial muscle into a new muscle with a different morphology by thermodynamic-twist coupling, and illustrate its structural evolution during actuation. The muscle length can be continuously modulated over a large temperature range, and actuation occurs by continuously changing the temperature. This strategy is applicable to different actuation modes, including tensile elongation, tensile contraction and torsional rotation. This is realized by twist insertion into a fibre to produce torsional stress. Fibre annealing causes partial thermodynamic relaxation of the spiral molecular chains, which serves as internal tethering and inhibits fibre twist release, thus producing a self-supporting artificial muscle that actuates under heating. At a sufficiently high temperature, further relaxation of the spiral molecular chains occurs, resulting in a new muscle with a different length. A structural study provides an understanding of the thermodynamic-twist coupling. This work provides a new design strategy for intelligent materials.

More Powerful Twistron Carbon Nanotube Yarn Mechanical Energy Harvesters.

Stretching a coiled carbon nanotube (CNT) yarn can provide large, reversible electrochemical capacitance changes, which convert mechanical energy to electricity. Here, it is shown that the performance of these "twistron" harvesters can be increased by optimizing the alignment of precursor CNT forests, plastically stretching the precursor twisted yarn, applying much higher tensile loads during precoiling twist than for coiling, using electrothermal pulse annealing under tension, and incorporating reduced graphene oxide nanoplates. The peak output power for a 1 and a 30 Hz sinusoidal deformation are 0.73 and 3.19 kW kg-1 , respectively, which are 24- and 13-fold that of previous twistron harvesters at these respective frequencies. This performance at 30 Hz is over 12-fold that of other prior-art mechanical energy harvesters for frequencies between 0.1 and 600 Hz. The maximum energy conversion efficiency is 7.2-fold that for previous twistrons. Twistron anode and cathode yarn arrays are stretched 180° out-of-phase by locating them in the negative and positive compressibility directions of hinged wine-rack frames, thereby doubling the output voltage and reducing the input mechanical energy.

The Power of Fiber Twist.

Nature's evolution over billions of years has led to the development of different kinds of twisted structures in a variety of biological species. Twisted fibers from nanoscale- to micrometer-scale diameter have been prepared by mimicking natural twisted structures. Mechanically inserting twist in a yarn is an efficient and important method, which generates internal stress, changes the macromolecular orientation, and increases compactness. Recently, twist insertion has been found to produce interesting fiber properties, including chemical, mechanical, electrical, and thermal properties. This Account summarizes recent progress in how twist insertion affects the chemical and physical properties of fibers and describes their applications in artificial spider silk, artificial muscles, refrigeration, and electricity generation.Twist and associated chirality widely arise in nature from molecules to nano- and microscale materials to macroscopic objects such as DNA, RNA, peptides, and chromosomes. Such twisted architectures play an important role in improving the mechanical properties and enabling biological functions. Inspired by the beauty and interesting properties of twisted structures, a wide range of artificial chiral materials with twisted or coiled structures have been prepared, from organic and inorganic nanorods, nanotubes, and nanobelts to macroscopic architectures and buildings.An efficient way to prepare twisted materials is by inserting twist in fibers or yarns, which is an ancient technique used to make yarns or ropes (Wang, R., et al. Science 2019, 366, 216-221. Mu, J., et al. Science 2019, 365, 150-155). During the twisting process, torque is generated in fibers or yarns, the structure of the polymer chains becomes helically oriented, and the fibers in a yarn become more compact. Therefore, the twisting of fibers and yarns can produce novel chemical, mechanical, electrical, and thermal properties (Dou, Y., et al. Nat. Commun. 2019, 10, 1-10. Kim, S. H., et al. Science 2017, 357, 773-778). This Account focuses on the novel properties generated by twist insertion. The mechanical stress and strain can be optimized in a yarn by twist insertion, and different types of fibers exhibit rather different mechanisms.In the first section, we will focus on recent progress in improving the mechanical properties of twisted fibers, including carbon nanotube yarns, single-filament fibers, and hydrogel fibers. Torque was generated by twist insertion in a fiber or a yarn, and the balance of internal torsional stress can be changed by causing a change in yarn volume. This will result in twist release and torsional and tensile actuations of the yarn, which will be described in the second section. Twisting a yarn generally makes it more compact, which will result in a mechanically induced change in capacitance, supercapacitance, and other useful electrochemical properties when a conducting yarn is in an electrolyte. Such processes were used to develop novel devices for twist-based electricity generation, called twistrons, which will be discussed in the third section. Twist insertion or release also changes the polymer chain orientation or crystal structure, resulting in changes in entropy. This is called the twistocaloric effect, which was used to develop a new cooling method, and will be discussed in the last section.

High-strength scalable graphene sheets by freezing stretch-induced alignment.

ABSTRACCT: Efforts to obtain high-strength graphene sheets by near-room-temperature assembly have been frustrated by the misalignment of graphene layers, which degrades mechanical properties. While in-plane stretching can decrease this misalignment, it reappears when releasing the stretch. Here we use covalent and π-π inter-platelet bridging to permanently freeze stretch-induced alignment of graphene sheets, and thereby increase isotropic in-plane sheet strength to 1.55 GPa, in combination with a high Young's modulus, electrical conductivity and weight-normalized shielding efficiency. Moreover, the stretch-bridged graphene sheets are scalable and can be easily bonded together using a commercial resin without appreciably decreasing the performance, which establishes the potential for practical applications.

Humidity- and Water-Responsive Torsional and Contractile Lotus Fiber Yarn Artificial Muscles.

Materials that dynamically respond to their environment have diverse applications in artificial muscles, soft robotics, and smart textiles. Inspired by biological systems, humidity- and water-responsive actuators that bend, twist, and contract have been previously demonstrated. However, more powerful artificial muscles with large strokes and high work densities are needed, especially those that can be made cost-effectively from eco-friendly materials. We here derive such muscles from naturally abundant lotus fibers. A coiled lotus fiber yarn muscle provides a large, reversible tensile stroke of 38% and a work capacity during contraction of 450 J/kg, which is 56 times higher than that of natural skeletal muscles and higher than that for any other reported natural fiber muscles. In addition, highly twisted lotus fiber yarn muscles provide a fully reversible torsional stroke of 200°/mm of muscle length and a peak rotation speed of 200 rpm, with a generated specific torque of 488 mN·m/kg for a 2.5 cm long muscle. Potential applications of these lotus fiber yarn muscles are demonstrated for a weight-lifting artificial limb and a smart textile.

Unipolar stroke, electroosmotic pump carbon nanotube yarn muscles.

Success in making artificial muscles that are faster and more powerful and that provide larger strokes would expand their applications. Electrochemical carbon nanotube yarn muscles are of special interest because of their relatively high energy conversion efficiencies. However, they are bipolar, meaning that they do not monotonically expand or contract over the available potential range. This limits muscle stroke and work capacity. Here, we describe unipolar stroke carbon nanotube yarn muscles in which muscle stroke changes between extreme potentials are additive and muscle stroke substantially increases with increasing potential scan rate. The normal decrease in stroke with increasing scan rate is overwhelmed by a notable increase in effective ion size. Enhanced muscle strokes, contractile work-per-cycle, contractile power densities, and energy conversion efficiencies are obtained for unipolar muscles.

Super-tough MXene-functionalized graphene sheets.

Flexible reduced graphene oxide (rGO) sheets are being considered for applications in portable electrical devices and flexible energy storage systems. However, the poor mechanical properties and electrical conductivities of rGO sheets are limiting factors for the development of such devices. Here we use MXene (M) nanosheets to functionalize graphene oxide platelets through Ti-O-C covalent bonding to obtain MrGO sheets. A MrGO sheet was crosslinked by a conjugated molecule (1-aminopyrene-disuccinimidyl suberate, AD). The incorporation of MXene nanosheets and AD molecules reduces the voids within the graphene sheet and improves the alignment of graphene platelets, resulting in much higher compactness and high toughness. In situ Raman spectroscopy and molecular dynamics simulations reveal the synergistic interfacial interaction mechanisms of Ti-O-C covalent bonding, sliding of MXene nanosheets, and π-π bridging. Furthermore, a supercapacitor based on our super-tough MXene-functionalized graphene sheets provides a combination of energy and power densities that are high for flexible supercapacitors.

Artificial spider silk from ion-doped and twisted core-sheath hydrogel fibres.

Spider silks show unique combinations of strength, toughness, extensibility, and energy absorption. To date, it has been difficult to obtain spider silk-like mechanical properties using non-protein approaches. Here, we report on an artificial spider silk produced by the water-evaporation-induced self-assembly of hydrogel fibre made from polyacrylic acid and silica nanoparticles. The artificial spider silk consists of hierarchical core-sheath structured hydrogel fibres, which are reinforced by ion doping and twist insertion. The fibre exhibits a tensile strength of 895 MPa and a stretchability of 44.3%, achieving mechanical properties comparable to spider silk. The material also presents a high toughness of 370 MJ m-3 and a damping capacity of 95%. The hydrogel fibre shows only ~1/9 of the impact force of cotton yarn with negligible rebound when used for impact reduction applications. This work opens an avenue towards the fabrication of artificial spider silk with applications in kinetic energy buffering and shock-absorbing.

Torsional refrigeration by twisted, coiled, and supercoiled fibers.

Higher-efficiency, lower-cost refrigeration is needed for both large- and small-scale cooling. Refrigerators using entropy changes during cycles of stretching or hydrostatic compression of a solid are possible alternatives to the vapor-compression fridges found in homes. We show that high cooling results from twist changes for twisted, coiled, or supercoiled fibers, including those of natural rubber, nickel titanium, and polyethylene fishing line. Using opposite chiralities of twist and coiling produces supercoiled natural rubber fibers and coiled fishing line fibers that cool when stretched. A demonstrated twist-based device for cooling flowing water provides high cooling energy and device efficiency. Mechanical calculations describe the axial and spring-index dependencies of twist-enhanced cooling and its origin in a phase transformation for polyethylene fibers.

Sheath-run artificial muscles.

Although guest-filled carbon nanotube yarns provide record performance as torsional and tensile artificial muscles, they are expensive, and only part of the muscle effectively contributes to actuation. We describe a muscle type that provides higher performance, in which the guest that drives actuation is a sheath on a twisted or coiled core that can be an inexpensive yarn. This change from guest-filled to sheath-run artificial muscles increases the maximum work capacity by factors of 1.70 to 2.15 for tensile muscles driven electrothermally or by vapor absorption. A sheath-run electrochemical muscle generates 1.98 watts per gram of average contractile power-40 times that for human muscle and 9.0 times that of the highest power alternative electrochemical muscle. Theory predicts the observed performance advantages of sheath-run muscles.

Controllable Preparation of Ordered and Hierarchically Buckled Structures for Inflatable Tumor Ablation, Volumetric Strain Sensor, and Communication via Inflatable Antenna.

Inflatable conducting devices providing improved properties and functionalities are needed for diverse applications. However, the difficult part in making high-performance inflatable devices is the enabling of two-dimensional (2D) buckles with controlled structures on inflatable catheters. Here, we report the fabrication of highly inflatable devices with controllable structures by wrapping the super-aligned carbon nanotube sheet (SACNS) on the pre-inflated catheter. The resulting structure exhibits unique 2D buckled structures including quasi-parallel buckles, crisscrossed buckles, and hierarchically buckled structures, which enables reversible structural changes of 7470% volumetric strain. The 2D SACNS buckled structures show stable electrical conductance and surface wettability during large strain inflation/deflation cycles. Inflatable devices including inflatable tumor ablation, capacitive volumetric strain sensor, and communication via inflatable radio frequency antenna based on these structures are demonstrated.

Large-Stroke Electrochemical Carbon Nanotube/Graphene Hybrid Yarn Muscles.

Artificial muscles are reported in which reduced graphene oxide (rGO) is trapped in the helical corridors of a carbon nanotube (CNT) yarn. When electrochemically driven in aqueous electrolytes, these coiled CNT/rGO yarn muscles can contract by 8.1%, which is over six times that of the previous results for CNT yarn muscles driven in an inorganic electrolyte (1.3%). They can contract to provide a final stress of over 14 MPa, which is about 40 times that of natural muscles. The hybrid yarn muscle shows a unique catch state, in which 95% of the contraction is retained for 1000 s following charging and subsequent disconnection from the power supply. Hence, they are unlike thermal muscles and natural muscles, which need to consume energy to maintain contraction. Additionally, these muscles can be reversibly cycled while lifting heavy loads.

Strong, Conductive, Foldable Graphene Sheets by Sequential Ionic and π Bridging.

The goal of this work is to develop an inexpensive low-temperature process that provides polymer-free, high-strength, high-toughness, electrically conducting sheets of reduced graphene oxide (rGO). To develop this process, we have evaluated the mechanical and electrical properties resulting from the application of an ionic bonding agent (Cr3+ ), a π-π bonding agent comprising pyrene end groups, and their combinations for enhancing the performance of rGO sheets. When only one bonding agent was used, the π-π bonding agent is much more effective than the ionic bonding agent for improving both the mechanical and electrical properties of rGO sheets. However, the successive application of ionic bonding and π-π bonding agents maximizes tensile strength, toughness, long-term electrical stability in various corrosive solutions, and resistance to mechanical abuse and ultrasonic dissolution. Using a combination of ionic bonding and π-π bonding agents, high tensile strength (821 MPa), high toughness (20 MJ m-3 ), and electrical conductivity (416 S cm-1 ) were obtained, as well as remarkable retention of mechanical and electrical properties during ultrasonication and mechanical cycling by both sheet stretch and sheet folding, suggesting high potential for applications in aerospace and flexible electronics.

Sequentially bridged graphene sheets with high strength, toughness, and electrical conductivity.

We here show that infiltrated bridging agents can convert inexpensively fabricated graphene platelet sheets into high-performance materials, thereby avoiding the need for a polymer matrix. Two types of bridging agents were investigated for interconnecting graphene sheets, which attach to sheets by either π-π bonding or covalent bonding. When applied alone, the π-π bonding agent is most effective. However, successive application of the optimized ratio of π-π bonding and covalent bonding agents provides graphene sheets with the highest strength, toughness, fatigue resistance, electrical conductivity, electromagnetic interference shielding efficiency, and resistance to ultrasonic dissolution. Raman spectroscopy measurements of stress transfer to graphene platelets allow us to decipher the mechanisms of property improvement. In addition, the degree of orientation of graphene platelets increases with increasing effectiveness of the bonding agents, and the interlayer spacing increases. Compared with other materials that are strong in all directions within a sheet, the realized tensile strength (945 MPa) of the resin-free graphene platelet sheets was higher than for carbon nanotube or graphene platelet composites, and comparable to that of commercially available carbon fiber composites. The toughness of these composites, containing the combination of π-π bonding and covalent bonding, was much higher than for these other materials having high strengths for all in-plane directions, thereby opening the path to materials design of layered nanocomposites using multiple types of quantitatively engineered chemical bonds between nanoscale building blocks.

Polar-Electrode-Bridged Electroluminescent Displays: 2D Sensors Remotely Communicating Optically.

A novel geometry for electroluminescent devices, which does not require transparent electrodes for electrical input, is demonstrated, theoretically analyzed, and experimentally characterized. Instead of emitting light through a conventional electrode, light emission occurs through a polar liquid or solid and input electrical electrodes are coplanar, rather than stacked in a sandwich configuration. This new device concept is scalable and easily deployed for a range of modular alternating-current-powered electroluminescent light sources and light-emitting sensing devices. The polar-electrode-bridged electroluminescent displays can be used as remotely readable, spatially responsive sensors that emit light in response to the accumulation and distribution of materials on the device surface. Using this device structure, various types of alternating current devices are demonstrated. These include an umbrella that automatically lights up when it rains, a display that emits light from regions touched by human fingers (or painted upon using a mixture of oil and water), and a sensor that lights up differently in different areas to indicate the presence of water and its freezing. This study extends the dual-stack, coplanar-electrode device geometry to provide displays that emit light from a figure drawn on an electroluminescent panel using a graphite pencil.