Engineering the Thermal Conductivity of Functional Phase‐Change Materials for Heat Energy Conversion,Storage, and Utilization

Thermal energy storage technologies based on phase‐change materials (PCMs) have received tremendous attention in recent years. These materials are capable of reversibly storing large amounts of thermal energy during the isothermal phase transition and offer enormous potential in the development of state‐of‐the‐art renewable energy infrastructure. Thermal conductivity plays a vital role in regulating the thermal charging and discharging rate of PCMs and improving the heat‐utilization efficiency. The strategies for tuning the thermal conductivity of PCMs and their potential energy applications, such as thermal energy harvesting and storage, thermal management of batteries, thermal diodes, and other forms of energy utilization, are summarized systematically. Furthermore, a research perspective is given to highlight emerging research directions of engineering advanced functional PCMs for energy applications.     

Semiconducting Carbon Nanotubes for Improved Efficiency and Thermal Stability of Polymer–Fullerene Solar Cells

The effects of the incorporation of semiconducting single‐walled nanotubes (sc‐SWNTs) with high purity on the bulk heterojunction (BHJ) organic solar cell (OSC) based on regioregular poly(3‐hexylthiophene‐2,5‐diyl):[6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (rr‐P3HT:PCBM) are reported for the first time. The sc‐SWNTs induce the organization of the polymer phase, which is evident from the increase in crystallite size, the red‐shifted absorption characteristics and the enhanced hole mobility. By incorporating sc‐SWNTs, OSC with a power conversion efficiency (PCE) as high as 4% can be achieved, which is ≈8% higher than our best control device. A novel application of sc‐SWNTs in improving the thermal stability of BHJ OSCs is also demonstrated. After heating at 150 °C for 9 h, it is observed that the thermal stability of rr‐P3HT:PCBM devices improves by more than fivefold with inclusion of sc‐SWNTs. The thermal stability enhancement is attributed to a more suppressed phase separation, as shown by the remarkable decrease in the formation of sizeable crystals, which in turn can be the outcome of a more controlled crystallization of the blend materials on the nanotubes.     

Monothiatruxene‐Based,Solution‐Processed Green,Sky‐Blue,and Deep‐Blue Organic Light‐Emitting Diodes with Efficiencies Beyond 5% Limit

The development of blue materials with good efficiency, even at high brightness, with excellent color purity, simple processing, and high thermal stability assuring adequate device lifetime is an important remaining challenge for organic light‐emitting didoes (OLEDs) in displays and lightning applications. Furthermore, these various features are typically mutually exclusive in practice. Herein, four novel green and blue light‐emitting materials based on a monothiatruxene core are reported together with their photophysical and thermal properties, and performance in solution‐processed OLEDs. The materials show excellent thermal properties with high glass transition temperatures ranging from 171 to 336 °C and decomposition temperatures from 352 to 442 °C. High external quantum efficiencies of 3.7% for a deep‐blue emitter with CIE color co‐ordinates (0.16, 0.09) and 7% for green emitter with color co‐ordinates (0.22, 0.40) are achieved at 100 cd m^?2. The efficiencies observed are exceptionally high for fluorescent materials with photoluminescence quantum yields of 24% and 62%, respectively. The performance at higher brightness is very good with only 38% and 17% efficiency roll‐offs at 1000 cd m^?2. The results indicate that utilization of this unique molecular design is promising for efficient deep‐blue highly stable and soluble light‐emitting materials.     

Carbon Fiber–Bismaleimide Composites Filled with Nickel‐Coated Single‐Walled Carbon Nanotubes for Lightning‐Strike Protection

Multifunctional carbon fiber composites are imperative for next‐generation lightweight aircraft structures. However, lightning‐strike protection is a feature that is lacking in many modern carbon fiber high‐temperature polymer systems, due to their high electrical resistivity. This work presents a study on processing, materials optimization, and property development of high‐temperature bismaleimide (BMI)–carbon fiber composites filled with nickel‐coated single‐walled carbon nanotubes (Ni‐SWNTs) based on three key factors: i) dispersion of Ni‐SWNTs, ii) their surface coverage on the carbon plies and, iii) the composite surface resistivity. Atomic force microscopy analysis revealed that coating purified SWNTs with nickel enabled improved dispersion which resulted in uniform surface coverage on the carbon plies. The electrical resistivity of the baseline composite system was reduced by ten orders of magnitude by the addition of 4 wt% Ni‐SWNTs (calculated with respect to the weight of a single carbon ply). Ni‐SWNT–filled composites showed a reduced amount of damage to simulated lightning strike compared to their unfilled counterparts, as indicated by the minimal carbon fiber pull‐out.     

Conversion‐Type MnO Nanorods as a Surprisingly Stable Anode Framework for Sodium‐Ion Batteries

The emergence of nanomaterials in the past decades has greatly advanced modern energy storage devices. Nanomaterials can offer high capacity and fast kinetics yet are prone to rapid morphological evolution and degradation. As a result, they are often hybridized with a stable framework in order to gain stability and fully utilize its advantages. However, candidates for such framework materials are rather limited, with carbon, conductive polymers, and Ti‐based oxides being the only choices; note these are all inactive or intercalation compounds. Conventionally, alloying‐/conversion‐type electrodes, which are thought to be electrochemically unstable by themselves, have never been considered as framework materials. This concept is challenged. Successful application of conversion‐type MnO nanorod as a anode framework for high‐capacity Mo₂C/MoO_x nanoparticles has been demonstrated in sodium‐ion batteries. Surprisingly, it can stably deliver 110 mAh g^?1 under extremely high rate of 8000 mA g^?1 (≈70 C) over 40 000 cycles with no capacity decay. More generally, this is considered as a proof of concept and much more alloying‐/conversion‐type materials are expected to be explored for such applications.     

Capacitive Enhancement Mechanisms and Design Principles of High‐Performance Graphene Oxide‐Based All‐Solid‐State Supercapacitors

Graphene oxide (GO)‐based all‐solid‐state supercapacitors (GO‐A3Ss) are superior over liquid electrolyte‐based supercapacitors and capable of being integrated on a single chip in various geometry shapes for the use of future smart wearable electronics field as a fast energy storage device, but their capacitance need to be improved. Here, a new approach has been developed for enhancing the capacitive capability of the supercapacitors through molecular dynamics simulations with the first‐principle input. A theoretical model of charge storage is developed to understand the unique capacitive enhancement mechanism and to predict the capacitance of the GO‐A3Ss, which agrees well with the experimental observations. A novel supercapacitor with GO and reduced graphene oxide (rGO) alternatively layered structures is designed based on the model, and its energy density is the highest among conventional supercapacitors using liquid electrolytes and all‐solid‐state supercapacitors using aerogels or hydrogels as the solid‐state electrolyte. Based on the predictions, two new types of high‐performance GO/rGO multilayered capacitors are proposed to meet different practical applications. The results of this work provide an approach for the design of high‐performance all‐solid‐state supercapacitors based on GO and rGO materials.     

Ultrathin Layered Hydroxide Cobalt Acetate Nanoplates Face‐to‐Face Anchored to Graphene Nanosheets for High‐Efficiency Lithium Storage

The dramatically increasing demand of high‐energy lithium‐ion batteries (LIBs) urgently requires advanced substitution for graphite‐based anodes. Herein, inspired from the extra capacity of lithium storage in solid‐electrolyte interface (SEI) films, layered hydroxide cobalt acetates (LHCA, Co(Ac)_0.48(OH)_1.52·0.55H₂O) are introduced as novel and high‐efficiency anode materials. Furthermore, ultrathin LHCA nanoplates are face‐to‐face anchored on the surface of graphene nanosheets (GNS) through a facile solvothermal method to improve the electronic transport and avoid agglomeration during repeated cycles. Profiting from the parallel structure, LHCA//GNS nanosheets exhibit extraordinary long‐term and high‐rate performance. At the current densities of 1000 and 4000 mA g^?1, the reversible capacities maintain ≈1050 mAh g^?1 after 200 cycles and ≈780 mAh g^?1 after 300 cycles, respectively, much higher than the theoretical value of LHCA according to the conversion mechanism. Fourier transform infrared spectroscopy confirms the conversion from acetate to acetaldehyde after lithiation. A reasonable mechanism is proposed to elucidate the lithium storage behaviors referring to the electrocatalytic conversion of OH groups with Co nanocatalysts. This work can help further understand the contribution of SEI components (especially LiOH and LiAc) to lithium storage. It is envisaged that layered transition metal hydroxides can be used as advanced materials for energy storage devices.     

Porous Carbons Derived from Collagen‐Enriched Biomass: Tailored Design,Synthesis, and Application in Electrochemical Energy Storage and Conversion

As byproducts of the meat‐processing industry, nearly 100 million tons of bones, skin, and scales are generated from livestock, poultry, and fish every year and are generally discarded as waste. However, these widespread and low‐cost biomass materials are rich in collagen that is primarily composed of the elements C, N, O, and S. By controlled pyrolysis, these collagen‐enriched biomass materials can be transformed into biomass‐derived porous carbons (BPCs). The ordered biotic structures and specific elemental compositions of the natural precursors endow BPCs with unique nanostructures and heteroatom doping, leading to promising applications in electrochemical energy storage and conversion. In particular, BPCs derived from animal bones and fish scales show novel porosities and morphologies due to their abundance of hydroxyapatite crystals, which act as naturally occurring nanostructured templates. Here, the first review focusing on the design and synthesis of collagen‐derived porous carbons (CPCs) is given. The specific applications of different CPCs in electrochemical energy storage and conversion are also summarized. Finally, the challenges and prospects for the controllable synthesis and large‐scale applications of CPCs are assessed.     

Baby Diaper‐Inspired Construction of 3D Porous Composites for Long‐Term Lithium‐Ion Batteries

In this paper, by using the superabsorbent polymers (SAPs) from baby diaper, the 3D porous composites decorated with NiO and Ni nanoparticles (NNSCs) have been prepared via a facile dissolving‐freeze drying and subsequent annealing reactions. The porous carbon matrix (PCM) derived from the SAPs also provides a continuous highly conductive network to facilitate the fast charge transfer and form a stable solid electrolyte interface film. Furthermore, NNSC can exhibit the high specific capacity and excellent cycle performance as anode materials for lithium‐ion batteries. And more importantly, employing the PCM derived from baby diaper offers a green approach for other energy storage materials.     

Self‐Propagating Domino‐like Reactions in Oxidized Graphite

Graphite oxide (GO) has received extensive interest as a precursor for the bulk production of graphene‐based materials. Here, the highly energetic nature of GO, noted from the self‐propagating thermal deoxygenating reaction observed in solid state, is explored. Although the resulting graphene product is quite stable against combustion even in a natural gas flame, its thermal stability is significantly reduced when contaminated with potassium salt by‐products left from GO synthesis. In particular, the contaminated GO becomes highly flammable. A gentle touch with a hot soldering iron can trigger violent, catastrophic, total combustion of such GO films, which poses a serious fire hazard. This highlights the need for efficient sample purification methods. Typically, purification of GO is hindered by its tendency to gelate as the pH value increases during rinsing. A two‐step, acid–acetone washing procedure is found to be effective for suppressing gelation and thus facilitating purification. Salt‐induced flammability is alarming for the fire safety of large‐scale manufacturing, processing, and storage of GO materials. However, the energy released from the deoxygenation of GO can also be harnessed to drive new reactions for creating graphene‐based hybrid materials. Through such domino‐like reactions, graphene sheets decorated with metal and metal oxide particles are synthesized using GO as the in situ power source. Enhanced electrochemical capacitance is observed for graphene sheets loaded with RuO₂ nanoparticles.     

Modular Layer‐by‐Layer Assembly of Polyelectrolytes,Nanoparticles, and Molecular Catalysts into Solar‐to‐Chemical Energy Conversion Devices

The design and fabrication of solar‐to‐chemical energy conversion devices are enabled through interweaving multiple components with various morphologies and unique functions using a versatile layer‐by‐layer assembly method. Cationic and anionic polyelectrolytes are used as an electrostatic adhesive to assemble the following functional materials: plasmonic Ag nanoparticles for improved light harvesting, upconversion nanoparticles for utilization of near‐infrared light, and polyoxometalate water oxidation catalysts for enhanced catalytic activity. Polyelectrolytes also have an additional function of passivating the surface recombination centers of the underlying photoelectrode. These functional components are precisely assembled on a model photoanode (e.g., Fe₂O₃ and BiVO₄) in a desired order and various combinations without degradation of their intrinsic properties. As a result, the performance of water oxidation photoanodes is synergistically enhanced. This study can enable the design and fabrication of novel solar‐to‐chemical energy conversion devices.     

Molecular‐Scale Hybridization of Clay Monolayers and Conducting Polymer for Thin‐Film Supercapacitors

Development of electrode materials with well‐defined architectures is a fruitful and profitable approach for achieving highly‐efficient energy storage systems. A molecular‐scale hybrid system is presented based on the self‐assembly of CoNi‐layered double hydroxide (CoNi‐LDH) monolayers and the conducting polymer (poly(3,4‐ethylene dioxythiophene):poly(styrene sulfonate), denoted as PEDOT:PSS) into an alternating‐layer superlattice. Owing to the homogeneous interface and intimate interaction, the resulting CoNi‐LDH/PEDOT:PSS hybrid materials possess a simultaneous enhancement in ion and charge‐carrier transport and exhibit improved capacitive properties with a high specific capacitance (960 F g^–1 at 2 A g^–1) and excellent rate capability (83.7% retention at 30 A g^–1). In addition, an in‐plane supercapacitor device with an interdigital design is fabricated based on a CoNi‐LDH/PEDOT:PSS thin film, delivering a significantly enhanced energy and power output (an energy density of 46.1 Wh kg^–1 at 11.9 kW kg^–1). Its application in miniaturized devices is further demonstrated by successfully driving a photodetector. These characteristics demonstrate that the molecular‐scale assembly of LDH monolayers and the conducting polymer is promising for energy storage and conversion applications in miniaturized electronics.     

Vanadium‐Based Nanomaterials: A Promising Family for Emerging Metal‐Ion Batteries

The emerging electrochemical energy storage systems beyond Li‐ion batteries, including Na/K/Mg/Ca/Zn/Al‐ion batteries, attract extensive interest as the development of Li‐ion batteries is seriously hindered by the scarce lithium resources. During the past years, large amounts of studies have focused on the investigation of various electrode materials toward emerging metal‐ion batteries to realize high energy density, high power density, and a long cycle life. In particular, vanadium‐based nanomaterials have received great attention. Vanadium‐based compounds have a big family with different structures, chemical compositions, and electrochemical properties, which provide huge possibilities for the development of emerging electrochemical energy storage. In this review, a comprehensive overview of the recent progresses of promising vanadium‐based nanomaterials for emerging metal‐ion batteries is presented. The vanadium‐based materials are classified into four groups: vanadium oxides, vanadates, vanadium phosphates, and oxygen‐free vanadium‐based compounds. The structures, electrochemical properties, and modification strategies are discussed. The structure–performance relationships and charge storage mechanisms are focused on. Finally, the perspectives about future directions of vanadium‐based nanomaterials for emerging energy storage devices are proposed. This review will provide comprehensive knowledge of vanadium‐based nanomaterials and shed light on their potential applications in emerging energy storage.     

Self‐Healing,Flexible, and Tailorable Triboelectric Nanogenerators for Self‐Powered Sensors based on Thermal Effect of Infrared Radiation

Self‐healing triboelectric nanogenerators (TENGs) with flexibility, robustness, and conformability are highly desirable for promising flexible and wearable devices, which can serve as a durable, stable, and renewable power supply, as well as a self‐powered sensor. Herein, an entirely self‐healing, flexible, and tailorable TENG is designed as a wearable sensor to monitor human motion, with infrared radiation from skin to promote self‐healing after being broken based on thermal effect of infrared radiation. Human skin is a natural infrared radiation emitter, providing favorable conditions for the device to function efficiently. The reversible imine bonds and quadruple hydrogen bonding (UPy) moieties are introduced into polymer networks to construct self‐healable electrification layer. UPy‐functionalized multiwalled carbon nanotubes are further incorporated into healable polymer to obtain conductive nanocomposite. Driven by the dynamic bonds, the designed and synthesized materials show excellent intrinsic self‐healing and shape‐tailorable features. Moreover, there is a robust interface bonding in the TENG devices due to the similar healable networks between electrification layer and electrode. The output electric performances of the self‐healable TENG devices can almost restore their original state when the damage of the devices occurs. This work presents a novel strategy for flexible devices, contributing to future sustainable energy and wearable electronics.     

Hierarchically Structured Porous Materials for Energy Conversion and Storage

Materials with hierarchical porosity and structures have been heavily involved in newly developed energy storage and conversion systems. Because of meticulous design and ingenious hierarchical structuration of porosities through the mimicking of natural systems, hierarchically structured porous materials can provide large surface areas for reaction, interfacial transport, or dispersion of active sites at different length scales of pores and shorten diffusion paths or reduce diffusion effect. By the incorporation of macroporosity in materials, light harvesting can be enhanced, showing the importance of macrochannels in light related systems such as photocatalysis and photovoltaics. A state‐of‐the‐art review of the applications of hierarchically structured porous materials in energy conversion and storage is presented. Their involvement in energy conversion such as in photosynthesis, photocatalytic H₂ production, photocatalysis, or in dye sensitized solar cells (DSSCs) and fuel cells (FCs) is discussed. Energy storage technologies such as Li‐ions batteries, supercapacitors, hydrogen storage, and solar thermal storage developed based on hierarchically porous materials are then discussed. The links between the hierarchically porous structures and their performances in energy conversion and storage presented can promote the design of the novel structures with advanced properties.     

Tungsten‐Based Materials for Lithium‐Ion Batteries

Lithium‐ion batteries are widely used as reliable electrochemical energy storage devices due to their high energy density and excellent cycling performance. The search for anode materials with excellent electrochemical performances remains critical to the further development of lithium‐ion batteries. Tungsten‐based materials are receiving considerable attention as promising anode materials for lithium‐ion batteries owing to their high intrinsic density and rich framework diversity. This review describes the advances of exploratory research on tungsten‐based materials (tungsten oxide, tungsten sulfide, tungsten diselenide, and their composites) in lithium‐ion batteries, including synthesis methods, microstructures, and electrochemical performance. Some personal prospects for the further development of this field are also proposed.     

Superplastic Air‐Dryable Graphene Hydrogels for Wet‐Press Assembly of Ultrastrong Superelastic Aerogels with Infinite Macroscale

Highly compressible graphene‐based monoliths with excellent mechanical, electrical, and thermal properties hold great potential as multifunctional structural materials to realize the targets of energy‐efficiency, comfort, and safety for buildings, vehicles, aircrafts, etc. Unfortunately, the ultralow mechanical strength and limited macroscale have hampered their practical applications. Herein, ultrastrong superelastic graphene aerogel with infinite macroscale is obtained by a facile wet‐press assembly strategy based on the novel superplastic air‐dryable graphene hydrogel (SAGH). The SAGH with isotropic, open‐cell, and highly porous microstructure is carefully designed by a dual‐template sol–gel method. Countless SAGH “bricks” can be assembled together orderly by press to form the strongly combined wet‐press assembled graphene aerogel (WAGA) “wall” after air‐drying. The WAGA with highly oriented, dense, multiple‐arch microstructure possesses arbitrary macroscale, outstanding compressive strength (47 MPa, over 10 times higher than the best ever reported), super elasticity (>97% strain), and high conductivity (378 S m^?1). The strong adhesion is attributed to the tightly face‐to‐face contacted graphene interfaces caused by wet‐press and air‐drying. The WAGAs prove to be excellent multifunctional structural materials in the fields of high pressure/strain sensor, tunable mechanical energy absorber, high‐performance fire‐resistance, and thermal insulation. This facile strategy is easily extended to fabricate other similar metamaterials.     

An Energy‐Dense Solvent‐Free Dual‐Ion Battery

Ever‐increasing energy demands call for alternative energy storage technologies with balanced performance and cost characteristics to meet current and emerging applications. Dual‐ion batteries (DIBs) are considered particularly attractive owing to the potentially high specific energy, a rich variety of charge carrier combinations, and the applicability of metal‐free cathode and earth‐abundant anode materials. However, their performance falls far below expectations because of a large excess of solvent needed to dissolve electroactive species that induces side reactions and contributes parasitic weight, which penalizes the reversible capacity and cell‐level energy density. Herein, a solvent‐free DIB utilizing a binary alkali metal molten salt based on bis(fluorosulfonyl)amide as the electrolyte to solve these issues is demonstrated. The cell (NaK‐DIB) operates in a temperature range of 90–120 °C and exhibits high theoretical energy densities of 246 Wh kg^?1 and 533 Wh L^?1 based on active materials and capacity‐matched electrolyte, far surpassing those of reported DIBs. Further improvements could realize affordable grid‐scale energy storage.     

Porous Iron–Cobalt Alloy/Nitrogen‐Doped Carbon Cages Synthesized via Pyrolysis of Complex Metal–Organic Framework Hybrids for Oxygen Reduction

Efficient and stable nonprecious metal electrocatalysts for oxygen reduction are of great significance in some important electrochemical energy storage and conversion systems. As a unique class of porous hybrid materials, metal–organic frameworks (MOFs) and their composites are recently considered as promising precursors to derive advanced functional materials with controlled structures and compositions. Here, an “MOF‐in‐MOF hybrid” confined pyrolysis strategy is developed for the synthesis of porous Fe–Co alloy/N‐doped carbon cages. A unique “MOF‐in‐MOF hybrid” architecture constructed from a Zn‐based MOF core and a Co‐based MOF hybrid shell encapsulated with FeOOH nanorods is first prepared, followed by a pyrolysis process to obtain a cage‐shaped hybrid material consisting of Fe–Co alloy nanocrystallites evenly distributed inside a porous N‐doped carbon microshell. Of note, this strategy can be extended to synthesize many other multifunctional “nanosubstrate‐in‐MOF hybrid” core–shelled structures. Benefiting from the structural and compositional advantages, the as‐derived hybrid cages exhibit superior electrocatalytic performance for the oxygen reduction reaction in alkaline solution. The present approach may provide some insight in design and synthesis of complex MOF hybrid structures and their derived functional materials for energy storage and conversion applications.     

Small‐Molecule‐Doped Organic Crystals with Long‐Persistent Luminescence

Traditional long‐persistent luminescence (LPL) materials, which are based on inorganic systems containing rare elements and with preparation temperatures of at least 1000 °C, exhibit afterglow times of more than 10 h and can be tuned for different applications. However, the development of this field is hindered due to the large thermal energy consumption and the need for nonrenewable resources. Thus, the development of a “green” design and preparation of LPL materials is of some importance. A doped‐crystalline material based on two metal‐free organic small molecules is easily prepared through ultrasonic crystallization at room temperature. It has a high‐quality, single‐crystalline structure, and visible LPL performance with a duration of more than 6 s upon low‐energy photoexcitation. A green, flexible, and convenient screen‐printing technology for controllable pattern anticounterfeiting is then developed from this purely organic material, which improves the prospects for commercial utilization in the future.