Ionic Organic Thermoelectrics with Impressively High Thermopower for Sensitive Heat Harvesting Scenarios

As the worldwide energy crisis is worsened, thermoelectric materials that can harvest low-grade waste heat and directly convert it into electricity provide promising alternative energy sources. Emerging ionic thermoelectrics (iTEs) have recently attracted widespread attention thanks to their impressively high thermopower that can reach hundreds of times more than conventional electronic thermoelectrics (eTEs). Based on the Soret effect, the performances of iTEs depend on the thermo-diffusion of mobile ions in electrolytes, resulting in electrical characteristics distinct from eTE materials and opening up additional potential applications of thermoelectrics. Among these materials, organics-based iTEs (i-OTEs) provide unique advantages such as low-cost, light-weight, and eco-friendliness, thereby offering more promising application scenarios that can utilize dissipated heat, for example, from human bodies or mobile devices. This concise review begins with the comparison of iTE and eTE, and then discusses their different mechanisms and applied devices in detail. Next, the recent advances of i-OTEs will be in-depth highlighted, including the merits and weaknesses of representative types of materials, effects of additives, and effective strategies for performance optimization. Finally, the state-of-the-art achievements of i-OTEs are summarized, and an overview is provided of the existing challenges and an outlook of prospective development and applications in future efforts.     

Liquid–Solid Interfacial Assemblies of Soft Materials for Functional Freestanding Layered Membrane–Based Devices toward Electrochemical Energy Systems

Freestanding layered membrane–based devices have broad applications in highly efficient energy‐storage/conversion systems. The liquid–solid interface is considered as a unique yet versatile interface for constructing such layered membrane–based devices. In this review, the authors outline recent developments in the fabrication of soft materials to functionalize layered devices from the aspect of liquid–solid interfacial assembly and engineering arts. Seven liquid–solid interfacial assembly strategies, including flow‐directed, superlattice, solvent‐casting, evaporation‐induced, dip‐coating, spinning, and electrospinning assemblies, are comprehensively highlighted with a focus on their synthetic pathways, formation mechanisms, and interface engineering strategies. Meanwhile, recent representative works on layered membrane–based devices for electrochemical energy applications are presented. Finally, challenges and opportunities of this research area are highlighted in order to stimulate future developments. This review not only offers comprehensive and practical approaches to assemble liquid–solid interfaces with soft materials for various important layered electrochemical energy devices but also sheds lights on fundamental insights by thoughtful discussions on performance enhancement mechanisms of these electrochemical energy systems.     

Graphene‐Based Nanocomposites for Energy Storage

Since the first report of using micromechanical cleavage method to produce graphene sheets in 2004, graphene/graphene‐based nanocomposites have attracted wide attention both for fundamental aspects as well as applications in advanced energy storage and conversion systems. In comparison to other materials, graphene‐based nanostructured materials have unique 2D structure, high electronic mobility, exceptional electronic and thermal conductivities, excellent optical transmittance, good mechanical strength, and ultrahigh surface area. Therefore, they are considered as attractive materials for hydrogen (H₂) storage and high‐performance electrochemical energy storage devices, such as supercapacitors, rechargeable lithium (Li)‐ion batteries, Li–sulfur batteries, Li–air batteries, sodium (Na)‐ion batteries, Na–air batteries, zinc (Zn)–air batteries, and vanadium redox flow batteries (VRFB), etc., as they can improve the efficiency, capacity, gravimetric energy/power densities, and cycle life of these energy storage devices. In this article, recent progress reported on the synthesis and fabrication of graphene nanocomposite materials for applications in these aforementioned various energy storage systems is reviewed. Importantly, the prospects and future challenges in both scalable manufacturing and more energy storage‐related applications are discussed.     

Hierarchical Structures Based on Two‐Dimensional Nanomaterials for Rechargeable Lithium Batteries

Two‐dimensional (2D) nanomaterials (i.e., graphene and its derivatives, transition metal oxides and transition metal dichalcogenides) are receiving a lot attention in energy storage application because of their unprecedented properties and great diversities. However, their re‐stacking or aggregation during the electrode fabrication process has greatly hindered their further developments and applications in rechargeable lithium batteries. Recently, rationally designed hierarchical structures based on 2D nanomaterials have emerged as promising candidates in rechargeable lithium battery applications. Numerous synthetic strategies have been developed to obtain hierarchical structures and high‐performance energy storage devices based on these hierarchical structure have been realized. This review summarizes the synthesis and characteristics of three styles of hierarchical architecture, namely three‐dimensional (3D) porous network nanostructures, hollow nanostructures and self‐supported nanoarrays, presents the representative applications of hierarchical structured nanomaterials as functional materials for lithium ion batteries, lithium‐sulfur batteries and lithium‐oxygen batteries, meanwhile sheds light particularly on the relationship between structure engineering and improved electrochemical performance; and provides the existing challenges and the perspectives for this fast emerging field.     

PCL-Based Composite Scaffold Matrices for Tissue Engineering Applications

Biomaterial-based scaffolds are important cues in tissue engineering (TE) applications. Recent advances in TE have led to the development of suitable scaffold architecture for various tissue defects. In this narrative review on polycaprolactone (PCL), we have discussed in detail about the synthesis of PCL, various properties and most recent advances of using PCL and PCL blended with either natural or synthetic polymers and ceramic materials for TE applications. Further, various forms of PCL scaffolds such as porous, films and fibrous have been discussed along with the stem cells and their sources employed in various tissue repair strategies. Overall, the present review affords an insight into the properties and applications of PCL in various tissue engineering applications.     

Progressive Regulation of Electrical and Thermal Transport Properties to High‐Performance CuInTe2 Thermoelectric Materials

p‐type CuInTe₂ thermoelectric (TE) materials are of great interest for applications in the middle temperature range because of their environmentally benign chemical component and stable phase under operating temperatures. In order to enhance their TE performance to compete with the Pb based TE materials, a progressive regulation of electrical and thermal transport properties has been employed in this work. Anion P and Sb substitution is used to tune the electrical transport properties of CuInTe₂ for the first time, leading to a sharp enhancement in power factor due to the reduction of electrical resistivity by acceptor doping and the increase of the Seebeck coefficient resulted from the improvement of density of states. Concurrently, In₂O₃ nanoinclusions are introduced through an in situ oxidation between CuInTe₂ and ZnO additives, rendering a great reduction in the thermal conductivity of CuInTe₂ by the extra phonon scattering. Then, by integrating the anion substitution and nanoinclusions, a high power factor of 1445 μW m^?1 K^?2 and enhanced ZT of 1.61 at 823 K are achieved in the CuInTe₂ based TE material. This implies that the synergistic regulation of electrical and thermal transport properties by anion substitution and in situ nanostructure is a very effective approach to improve the TE performance of CuInTe₂ compounds.     

High‐Performance GeTe‐Based Thermoelectrics: from Materials to Devices

High‐performance GeTe‐based thermoelectrics have been recently attracting growing research interest. Here, an overview is presented of the structural and electronic band characteristics of GeTe. Intrinsically, compared to low‐temperature rhombohedral GeTe, the high‐symmetry and high‐temperature cubic GeTe has a low energy offset between L and Σ points of the valence band, the reduced direct bandgap and phonon group velocity, and as a result, high thermoelectric performance. Moreover, their thermoelectric performance can be effectively enhanced through either carrier concentration optimization, band structure engineering (bandgap reduction, band degeneracy, and resonant state engineering), or restrained lattice thermal conductivity (phonon velocity reduction or phonon scattering). Consequently, the dimensionless figure of merit, ZT values, of GeTe‐based thermoelectric materials can be higher than 2. The mechanical and thermal stabilities of GeTe‐based thermoelectrics are highlighted, and it is found that they are suitable for practical thermoelectric applications except for their high cost. Finally, it is recognized that the performance of GeTe‐based materials can be further enhanced through synergistic effects. Additionally, proper material selection and module design can further boost the energy conversion efficiency of GeTe‐based thermoelectrics.     

Polymer‐based microparticles in tissue engineering and regenerative medicine

Different types of biomaterials, processed into different shapes, have been proposed as temporary support for cells in tissue engineering (TE) strategies. The manufacturing methods used in the production of particles in drug delivery strategies have been adapted for the development of microparticles in the fields of TE and regenerative medicine (RM). Microparticles have been applied as building blocks and matrices for the delivery of soluble factors, aiming for the construction of TE scaffolds, either by fusion giving rise to porous scaffolds or as injectable systems for in situ scaffold formation, avoiding complicated surgery procedures. More recently, organ printing strategies have been developed by the fusion of hydrogel particles with encapsulated cells, aiming the production of organs in in vitro conditions. Mesoscale self‐assembly of hydrogel microblocks and the use of leachable particles in three‐dimensional (3D) layer‐by‐layer (LbL) techniques have been suggested as well in recent works. Along with innovative applications, new perspectives are open for the use of these versatile structures, and different directions can still be followed to use all the potential that such systems can bring. This review focuses on polymeric microparticle processing techniques and overviews several examples and general concepts related to the use of these systems in TE and RE applications. The use of materials in the development of microparticles from research to clinical applications is also discussed. © 2011 American Institute of Chemical Engineers Biotechnol. Prog., 2011     

Waste Recycling in Thermoelectric Materials

Thermoelectric (TE) technology enables the efficient conversion of waste heat generated in homes, transport, and industry into promptly accessible electrical energy. Such technology is thus finding increasing applications given the focus on alternative sources of energy. However, the synthesis of TE materials relies on costly and scarce elements, which are also environmentally damaging to extract. Moreover, spent TE modules lead to a waste of resources and cause severe pollution. To address these issues, many laboratory studies have explored the synthesis of TE materials using wastes and the recovery of scarce elements from spent modules, e.g., utilization of Si slurry as starting materials, development of biodegradable TE papers, and bacterial recovery and recycling of tellurium from spent TE modules. Yet, the outcomes of such work have not triggered sustainable industrial practices to the extent needed. This paper provides a systematic overview of the state of the art with a view to uncovering the opportunities and challenges for expanded application. Based on this overview, it explores a framework for synthesizing TE materials from waste sources with efficiencies comparable to those made from raw materials.     

Hollow Carbon Spheres and Their Hybrid Nanomaterials in Electrochemical Energy Storage

Electrochemical energy storage is of extraordinary importance for fulfilling the utilization of renewable and sustainable energy sources. There is an increasing demand for energy storage devices with high energy and power densities, prolonged stability, safety, and low cost. In the past decade, numerous research efforts have been devoted to achieving these requirements, especially in the design of advanced electrode materials. Hollow carbon spheres (HCS) derived nanomaterials combining the advantages of 3D HCS and porous structures have been considered as alternative electrode materials for advanced energy storage applications, due to their unique features such as high surface‐to‐volume ratios, encapsulation capability, together with outstanding chemical and thermal stability. In this review, the authors first present a comprehensive overview of the synthetic strategies of HCS, and elucidate the design and synthesis of HCS‐derived nanomaterials including various types of HCS and their nanohybrids. Additionally, their significant roles as electrode materials for supercapacitors, lithium‐ion or sodium‐ion batteries, and sulfur hosts for lithium sulfur batteries are highlighted. Finally, current challenges in the synthesis of HCS and future directions in HCS‐derived nanomaterials for energy storage applications are proposed.     

High‐Performance Thermoelectric Paper Based on Double Carrier‐Filtering Processes at Nanowire Heterojunctions

As commercial interest in flexible power‐conversion devices increases, the demand for high‐performance alternatives to brittle inorganic thermoelectric (TE) materials is growing. As an alternative, we propose a rationally designed graphene/polymer/inorganic nanocrystal free‐standing paper with high TE performance, high flexibility, and mechanical/chemical durability. The ternary hybrid system of the graphene/polymer/inorganic nanocrystal includes two hetero­junctions that induce double‐carrier filtering, which significantly increases the electrical conductivity without a major decrease in the thermopower. The ternary hybrid shows a power factor of 143 μW m^?1 K^?1 at 300 K, which is one to two orders of magnitude higher than those of single‐ or binary‐component materials. In addition, with five hybrid papers and polyethyleneimine (PEI)‐doped single‐walled carbon nanotubes (SWCNTs) as the p‐type and n‐type TE units, respectively, a maximum power density of 650 nW cm^?2 at a temperature difference of 50 K can be obtained. The strategy proposed here can improve the performance of flexible TE materials by introducing more heterojunctions and optimizing carrier transfer at those junctions, and shows great potential for the preparation of flexible or wearable power‐conversion devices.     

Effect of Dislocation Arrays at Grain Boundaries on Electronic Transport Properties of Bismuth Antimony Telluride: Unified Strategy for High Thermoelectric Performance

Taming electronic and thermal transport properties is the ultimate goal in the quest to achieve unprecedentedly high performance in thermoelectric (TE) materials. Most state‐of‐the‐art TE materials are inherently narrow bandgap semiconductors, which have an inevitable contribution from minority carriers, concurrently decreasing Seebeck coefficient and increasing thermal conductivity. Nevertheless, the restraint control of minority carrier transport is seldom considered as a key element to enhance the TE figure of merit (zT). Herein, it is verified that the localized dislocation arrays at grain boundaries enable the suppression of minority carrier contribution to electronic transport properties, resulting in an increase of the Seebeck coefficient and the carrier mobility in bismuth antimony tellurides. It is also suggested that the suppression of minority carriers via the generation of dislocation arrays at grain boundaries is an effective and noninvasive strategy to optimize overall electronic transport properties without sacrificing predominant characteristics of majority carriers in TE materials.     

Hybrid Perovskites: Effective Crystal Growth for Optoelectronic Applications

Outstanding material properties of organic‐inorganic hybrid perovskites have triggered a new insight into the next‐generation solar cells. Beyond solar cells, a wide range of controllable properties of hybrid perovskites, particularly depending on crystal growth conditions, enables versatile high‐performance optoelectronic devices such as light‐emitting diodes, photodetectors, and lasers. This article highlights recent progress in the crystallization strategies of organic–inorganic hybrid perovskites for use as effective light harvesters or light emitters. Fundamental background on perovskite crystalline structures and relevant optoelectronic properties such as optical band‐gap, electron‐hole behavior, and energy band alignment are given. A detailed overview of the effective crystallization methods for perovskites, including thermal treatment, additives, solvent mediator, laser irradiation, nanostructure, and crystal dimensionalityis reported offering a comprehensive correlation among perovskite processing conditions, crystalline morphology, and relevant device performance. Finally, future research directions to overcome current practical bottlenecks and move towards reliable high performance perovskite optoelectronic applications are proposed.     

Fiber‐Based Thermoelectric Generators: Materials,Device Structures,Fabrication, Characterization,and Applications

Fiber‐based flexible thermoelectric energy generators are 3D deformable, lightweight, and desirable for applications in large‐area waste heat recovery, and as energy suppliers for wearable or mobile electronic systems in which large mechanical deformations, high energy conversion efficiency, and electrical stability are greatly demanded. These devices can be manufactured at low or room temperature under ambient conditions by established industrial processes, offering cost‐effective and reliable products in mass quantity. This article presents a critical overview and review of state‐of‐the‐art fiber‐based thermoelectric generators, covering their operational principle, materials, device structures, fabrication methods, characterization, and potential applications. Scientific and practical challenges along with critical issues and opportunities are also discussed.     

Advanced Electrode Materials Comprising of Structure‐Engineered Quantum Dots for High‐Performance Asymmetric Micro‐Supercapacitors

Micro‐supercapacitors (MSCs) as a new class of energy storage devices have attracted great attention due to their unique merits. However, the narrow operating voltage, slow frequency response, and relatively low energy density of MSCs are still insufficient. Therefore, an effective strategy to improve their electrochemical performance by innovating upon the design from various aspects remains a huge challenge. Here, surface and structural engineering by downsizing to quantum dot scale, doping heteroatoms, creating more structural defects, and introducing rich functional groups to two dimensional (2D) materials is employed to tailor their physicochemical properties. The resulting nitrogen‐doped graphene quantum dots (N‐GQDs) and molybdenum disulfide quantum dots (MoS₂‐QDs) show outstanding electrochemical performance as negative and positive electrode materials, respectively. Importantly, the obtained N‐GQDs//MoS₂‐QDs asymmetric MSCs device exhibits a large operating voltage up to 1.5 V (far exceeding that of most reported MSCs), an ultrafast frequency response (with a short time constant of 0.087 ms), a high energy density of 0.55 mWh cm^?3, and long‐term cycling stability. This work not only provides a novel concept for the design of MSCs with enhanced performance but also may have broad application in other energy storage and conversion devices based on QDs materials.     

High Band Degeneracy Contributes to High Thermoelectric Performance in p‐Type Half‐Heusler Compounds

Half‐Heusler (HH) compounds are important high temperature thermoelectric (TE) materials and have attracted considerable attention in the recent years. High figure of merit zT values of 0.8 to 1.0 have been obtained in n‐type ZrNiSn‐based HH compounds. However, developing high performance p‐type HH compounds are still a big challenge. Here, it is shown that a new p‐type HH alloy with a high band degeneracy of 8, Ti‐doped FeV_0.6Nb_0.4Sb, can achieve a high zT of 0.8, which is one of the highest reported values in the p‐type HH compounds. Although the band effective mass of this system is found to be high, which may lead to a low mobility, its low deformation potential and low alloy scattering potential both contribute to a reasonably high mobility. The enhanced phonon scattering by alloying leads to a reduced lattice thermal conductivity. The achieved high zT demonstrates that the p‐type Ti doped FeV_0.6Nb_0.4Sb HH alloys are promising as TE materials and offer an excellent TE performance match with n‐type ones for high temperature power generation.     

Half‐Heusler Thermoelectric Module with High Conversion Efficiency and High Power Density

Half‐Heusler (HH) compounds have shown great potential in waste heat recovery. Among them, p‐type NbFeSb and n‐type ZrNiSn based alloys have exhibited the best thermoelectric (TE) performance. However, TE devices based on NbFeSb‐based HH compounds are rarely studied. In this work, bulk volumes of p‐type (Nb_0.8Ta_0.2)_0.8Ti_0.2FeSb and n‐type Hf_0.5Zr_0.5NiSn_0.98Sb_0.02 compounds are successfully prepared with good phase purity, compositional homogeneity, and matchable TE performance. The peak zTs are higher than 1.0 at 973 K for Hf_0.5Zr_0.5NiSn_0.98Sb_0.02 and at 1200 K for (Nb_0.8Ta_0.2)_0.8Ti_0.2FeSb. Based on an optimal design by a full‐parameters 3D finite element model, a single stage TE module with 8 n‐p HH couples is assembled. A high conversion efficiency of 8.3% and high power density of 2.11 W cm^?2 are obtained when hot and cold side temperatures are 997 and 342 K, respectively. Compared to the previous TE module assembled by the same materials, the conversion efficiency is enhanced by 33%, while the power density is almost the same. Given the excellent mechanical robustness and thermal stability, matchable thermal expansion coefficient and TE properties of NbFeSb and ZrNiSn based HH alloys, this work demonstrates their great promise for power generation with both high conversion efficiency and high power density.     

Control of Mesoscale Morphology and Photovoltaic Performance in Diketopyrrolopyrrole‐Based Small Band Gap Terpolymers

Morphology control is one of the key strategies in optimizing the performance of organic photovoltaic materials, particularly for diketopyrrolopyrrole (DPP)‐based donor polymers. The design of DPP‐based polymers that provide high power conversion efficiency (PCE) presents a significant challenge that requires optimization of both energetics and morphology. Herein, a series of high performance, small band gap DPP‐based terpolymers are designed via two‐step side chain engineering, namely introducing alternating short and long alkyls for reducing the domain spacing and inserting alkylthio for modulating the energy levels. The new DPP‐based terpolymers are compared to delineate how the side chain impacts the mesoscale morphology. By employing the alkylthio‐substituted terpolymer PBDPP‐TS, the new polymer solar cell (PSC) device realizes a good balance of a high V _oc of 0.77 V and a high J _sc over 15 mA cm^?2, and thus realizes desirable PCE in excess of 8% and 9.5% in single junction and tandem PSC devices, respectively. The study indicates better control of domain purity will greatly improve performance of single junction DPP‐based PSCs toward 10% efficiency. More significantly, the utility of this stepwise side chain engineering can be readily expanded to other classes of well‐defined copolymers and triggers efficiency breakthroughs in novel terpolymers for photovoltaic and related electronic applications.     

Chiroptical property tuning of supramolecular assemblies in polymer matrices

Chiroptical materials have received much attention in diverse fields for applications such as displays, sensors, smart memory devices, and catalysis. Here, we develop a simple fabrication method for polymer films with tunable chiroptical properties using small amounts of self-assembling fluorescent dye as an additive. Both the circular dichroism and circularly polarized luminescence signals of the film can be tuned between positive and negative values by thermal treatment. The chiroptical properties can be varied by slight changes in the orientation of chiral pyrene moieties in self-assembled nanofibril networks.     

The Development of Pseudocapacitor Electrodes and Devices with High Active Mass Loading

Pseudocapacitive materials are used for supercapacitor applications due to their exceptionally high capacitance and low cost. Good capacitive performance of the pseudocapacitive materials at high active mass loadings is vital for the development of the next generation of supercapacitor devices. This review describes recent advances in materials and nanotechnologies, which allows the development of advanced pseudocapacitive devices with high active mass. An important breakthrough is the discovery of novel dispersing and capping agents for the colloidal processing of nanoparticles. Particularly important are novel co‐dispersants that exhibit enhanced adsorption on materials of different types, such as inorganic nanoparticles, carbon nanotubes, and graphene. Conceptually new strategies are designed to fabricate coated particles. Recent innovations pave the way for the development of multifunctional redox‐active dopants‐dispersants and dopants‐oxidants to manufacture conductive polymer composites. Among the most important advances in nanotechnology is the development of template methods and heterocoagulation techniques for composite manufacturing. The progress in the design of novel surface modification techniques and materials, discovery of advanced anchoring groups, and development of liquid–liquid extraction allows agglomerate‐free processing of nanomaterials and composites. This review describes fundamental aspects of novel technologies and their applications in the manufacturing of pseudocapacitive devices for energy storage.