Inorganic-Based Printed Thermoelectric Materials and Devices

One of the simplest ways to generate electric power from waste heat is thermoelectric (TE) energy conversion. So far, most of the research on thermoelectrics has focused on inorganic bulk TE materials and their device applications. However, high production costs per power output and limited shape conformity hinder applications of state-of-the-art thermoelectric devices (TEDs). In recent years, printed thermoelectrics has emerged as an exciting pathway for their potential in the production of low-cost shape-conformable TEDs. Although several inorganic bulk TE materials with high performance are successfully developed, achieving high performance in inorganic-based printed TE materials is still a challenge. Nevertheless, significant progress has been made in printed thermoelectrics in recent years. In this review article, it is started with an introduction signifying the importance of printed thermoelectrics followed by a discussion of theoretical concepts of thermoelectricity, from fundamental transport phenomena to device efficiency. Afterward, the general process of inorganic TE ink formulation is summarized, and the current development of the inorganic and hybrid inks with the mention of their TE properties and their influencing factors is elaborated. In the end, TEDs with different architecture and geometries are highlighted by documenting their performance and fabrication techniques.     

Elevated‐Temperature 3D Printing of Hybrid Solid‐State Electrolyte for Li‐Ion Batteries

While 3D printing of rechargeable batteries has received immense interest in advancing the next generation of 3D energy storage devices, challenges with the 3D printing of electrolytes still remain. Additional processing steps such as solvent evaporation were required for earlier studies of electrolyte fabrication, which hindered the simultaneous production of electrode and electrolyte in an all‐3D‐printed battery. Here, a novel method is demonstrated to fabricate hybrid solid‐state electrolytes using an elevated‐temperature direct ink writing technique without any additional processing steps. The hybrid solid‐state electrolyte consists of solid poly(vinylidene fluoride‐hexafluoropropylene) matrices and a Li⁺‐conducting ionic‐liquid electrolyte. The ink is modified by adding nanosized ceramic fillers to achieve the desired rheological properties. The ionic conductivity of the inks is 0.78 × 10 ^?3 S cm^?1. Interestingly, a continuous, thin, and dense layer is discovered to form between the porous electrolyte layer and the electrode, which effectively reduces the interfacial resistance of the solid‐state battery. Compared to the traditional methods of solid‐state battery assembly, the directly printed electrolyte helps to achieve higher capacities and a better rate performance. The direct fabrication of electrolyte from printable inks at an elevated temperature will shed new light on the design of all‐3D‐printed batteries for next‐generation electronic devices.     

Universal Nanocarrier Ink Platform for Biomaterials Additive Manufacturing

Ink engineering is a fundamental area of research within additive manufacturing (AM) that designs next‐generation biomaterials tailored for additive processes. During the design of new inks, specific requirements must be considered, such as flowability, postfabrication stability, biointegration, and controlled release of therapeutic molecules. To date, many (bio)inks have been developed; however, few are sufficiently versatile to address a broad range of applications. In this work, a universal nanocarrier ink platform is presented that provides tailored rheology for extrusion‐based AM and facilitates the formulation of biofunctional inks. The universal nanocarrier ink (UNI) leverages reversible polymer–nanoparticle interactions to form a transient physical network with shear‐thinning and self‐healing properties engineered for direct ink writing (DIW). The unique advantage of the material is that a range of functional secondary polymers can be combined with the UNI to enable stabilization of printed constructs via secondary cross‐linking as well as customized biofunctionality for tissue engineering and drug delivery applications. Specific UNI formulations are used for bioprinting of living tissue constructs and DIW of controlled release devices. The robust and versatile nature of the UNI platform enables rapid formulation of a broad range of functional inks for AM of advanced biomaterials.     

3D Printed Polymer Photodetectors

Extrusion‐based 3D printing, an emerging technology, has been previously used in the comprehensive fabrication of light‐emitting diodes using various functional inks, without cleanrooms or conventional microfabrication techniques. Here, polymer‐based photodetectors exhibiting high performance are fully 3D printed and thoroughly characterized. A semiconducting polymer ink is printed and optimized for the active layer of the photodetector, achieving an external quantum efficiency of 25.3%, which is comparable to that of microfabricated counterparts and yet created solely via a one‐pot custom built 3D‐printing tool housed under ambient conditions. The devices are integrated into image sensing arrays with high sensitivity and wide field of view, by 3D printing interconnected photodetectors directly on flexible substrates and hemispherical surfaces. This approach is further extended to create integrated multifunctional devices consisting of optically coupled photodetectors and light‐emitting diodes, demonstrating for the first time the multifunctional integration of multiple semiconducting device types which are fully 3D printed on a single platform. The 3D‐printed optoelectronic devices are made without conventional microfabrication facilities, allowing for flexibility in the design and manufacturing of next‐generation wearable and 3D‐structured optoelectronics, and validating the potential of 3D printing to achieve high‐performance integrated active electronic materials and devices.     

Highly Concentrated,Ultrathin Nickel Hydroxide Nanosheet Ink for Wearable Energy Storage Devices

Solution‐based techniques are considered as a promising strategy for scalable fabrication of flexible electronics owing to their low‐cost and high processing speed. The key to the success of these techniques is dominated by the ink formulation of active nanomaterials. This work successfully prepares a highly concentrated two dimensional (2D) crystal ink comprised of ultrathin nickel hydroxide (Ni(OH)₂) nanosheets with an average lateral size of 34 nm. The maximum concentration of Ni(OH)₂ nanosheets in water without adding any additives reaches as high as 50 mg mL^?1, which can be printed on arbitrary substrates to form Ni(OH)₂ thin films. As a proof‐of‐concept application, Ni(OH)₂ nanosheet ink is coated on commercialized carbon fiber yarns to fabricate wearable energy storage devices. The thus‐fabricated hybrid supercapacitors exhibit excellent flexibility with a capacitance retention of 96% after 5000 bending–unbending cycles, and good weavability with a high volumetric capacitance of 36.3 F cm^?3 at a current density of 0.4 A cm^?3, and an energy density of 11.3 mWh cm^?3 at a power density of 0.3 W cm^?3. As a demonstration of practical application, a red light emitting diode can be lighted up by three hybrid devices connected in series.     

3D Printing of Liquid Crystal Elastomeric Actuators with Spatially Programed Nematic Order

Liquid crystal elastomers (LCEs) are soft materials capable of large, reversible shape changes, which may find potential application as artificial muscles, soft robots, and dynamic functional architectures. Here, the design and additive manufacturing of LCE actuators (LCEAs) with spatially programed nematic order that exhibit large, reversible, and repeatable contraction with high specific work capacity are reported. First, a photopolymerizable, solvent‐free, main‐chain LCE ink is created via aza‐Michael addition with the appropriate viscoelastic properties for 3D printing. Next, high operating temperature direct ink writing of LCE inks is used to align their mesogen domains along the direction of the print path. To demonstrate the power of this additive manufacturing approach, shape‐morphing LCEA architectures are fabricated, which undergo reversible planar‐to‐3D and 3D‐to‐3D′ transformations on demand, that can lift significantly more weight than other LCEAs reported to date.     

基于光敏浆料的直写精细无模三维成型

配制了一种具有光敏特性的陶瓷浆料, 并用此浆料通过直写精细无模三维成型技术制备了线条直径为300μm的BaTiO3陶瓷基木堆结构. 系统地讨论了光敏浆料的配制方法、浆料直写无模成型的工作原理以及采用的烧结工艺. 制备过程中不同阶段的研究表明, 光敏浆料中的BaTiO₃纳米颗粒在烧结前未发生团聚, 从而保证挤压成型顺利进行; 烧结后样品成瓷效果好, 各向收缩均匀, 整体无变形、开裂. 该技术具有成型速度快、制造周期短、可用材料范围广等特点.     

Dewetting of conducting polymer inkjet droplets on patterned surfaces

The manufacture of high-performance electronic devices with micrometre or even submicrometre dimensions by solution processing and direct printing, requires the ability to control accurately the flow and spread of functional liquid inks on surfaces. This can be achieved with the help of surface-energy patterns causing inks to be repelled and dewetted from pre-defined regions of the substrate. To exploit this principle for the fabrication of submicrometre device structures, a detailed understanding of the factors causing ink droplets to dewet on patterned surfaces is required. Here, we use hydrophobic surface-energy barriers of different geometries to study the influence of solution viscosity, ink volume, and contact angle on the process of dewetting of inkjet-printed droplets of a water-based conducting polymer. We demonstrate polymer field-effect transistor devices with channel length of 500 nm fabricated by surface-energy-assisted inkjet printing.     

Chemically Integrated Inorganic‐Graphene Two‐Dimensional Hybrid Materials for Flexible Energy Storage Devices

State‐of‐the‐art energy storage devices are capable of delivering reasonably high energy density (lithium ion batteries) or high power density (supercapacitors). There is an increasing need for these power sources with not only superior electrochemical performance, but also exceptional flexibility. Graphene has come on to the scene and advancements are being made in integration of various electrochemically active compounds onto graphene or its derivatives so as to utilize their flexibility. Many innovative synthesis techniques have led to novel graphene‐based hybrid two‐dimensional nanostructures. Here, the chemically integrated inorganic‐graphene hybrid two‐dimensional materials and their applications for energy storage devices are examined. First, the synthesis and characterization of different kinds of inorganic‐graphene hybrid nanostructures are summarized, and then the most relevant applications of inorganic‐graphene hybrid materials in flexible energy storage devices are reviewed. The general design rules of using graphene‐based hybrid 2D materials for energy storage devices and their current limitations and future potential to advance energy storage technologies are also discussed.     

Recent Development of Printed Micro-Supercapacitors: Printable Materials,Printing Technologies,and Perspectives

The rapid progression of portable and wearable electronics has necessitated the development of high-performing, miniaturized energy-storage devices with flexible form factors and high energy and power delivery. Printed micro-supercapacitors (MSCs), with in-plane interdigital configurations, is touted as a promising choice to fulfill these requirements. New printing technologies can assemble MSCs with fiscal and environmental benefits, large form factors, and at high throughputs, qualities not afforded with conventional microfabrication technologies. Here, recent progress in the preparation of functional ink systems for wearable MSCs, encompassing electrode materials, conductor materials, and electrolytes, is presented. First, a comprehensive background of the fundamentals of printing technology is introduced, with discussions focusing on methods of improving ink functionality while simultaneously retaining good printability. Second, various printing techniques to ensure manufacturable scaling of wearable MSCs with high areal electrochemical performance and small footprint are explored. Within the scope of these two topics, various issues that hinder the full materialization of widespread adoption of printed MSC and next steps to overcome these issues are discussed. Further deep dives in scientific and technical challenges are also presented, including limited functionality of the inks, low printing resolution, overlay accuracy, and complex encapsulation.     

Carbon‐Nanotube‐Based Thermoelectric Materials and Devices

Conversion of waste heat to voltage has the potential to significantly reduce the carbon footprint of a number of critical energy sectors, such as the transportation and electricity‐generation sectors, and manufacturing processes. Thermal energy is also an abundant low‐flux source that can be harnessed to power portable/wearable electronic devices and critical components in remote off‐grid locations. As such, a number of different inorganic and organic materials are being explored for their potential in thermoelectric‐energy‐harvesting devices. Carbon‐based thermoelectric materials are particularly attractive due to their use of nontoxic, abundant source‐materials, their amenability to high‐throughput solution‐phase fabrication routes, and the high specific energy (i.e., W g^?1) enabled by their low mass. Single‐walled carbon nanotubes (SWCNTs) represent a unique 1D carbon allotrope with structural, electrical, and thermal properties that enable efficient thermoelectric‐energy conversion. Here, the progress made toward understanding the fundamental thermoelectric properties of SWCNTs, nanotube‐based composites, and thermoelectric devices prepared from these materials is reviewed in detail. This progress illuminates the tremendous potential that carbon‐nanotube‐based materials and composites have for producing high‐performance next‐generation devices for thermoelectric‐energy harvesting.     

Progress in 3D Printing of Carbon Materials for Energy‐Related Applications

The additive‐manufacturing (AM) technique, known as three‐dimensional (3D) printing, has attracted much attention in industry and academia in recent years. 3D printing has been developed for a variety of applications. Printable inks are the most important component for 3D printing, and are related to the materials, the printing method, and the structures of the final 3D‐printed products. Carbon materials, due to their good chemical stability and versatile nanostructure, have been widely used in 3D printing for different applications. Good inks are mainly based on volatile solutions having carbon materials as fillers such as graphene oxide (GO), carbon nanotubes (CNT), carbon blacks, and solvent, as well as polymers and other additives. Studies of carbon materials in 3D printing, especially GO‐based materials, have been extensively reported for energy‐related applications. In these circumstances, understanding the very recent developments of 3D‐printed carbon materials and their extended applications to address energy‐related challenges and bring new concepts for material designs are becoming urgent and important. Here, recent developments in 3D printing of emerging devices for energy‐related applications are reviewed, including energy‐storage applications, electronic circuits, and thermal‐energy applications at high temperature. To close, a conclusion and outlook are provided, pointing out future designs and developments of 3D‐printing technology based on carbon materials for energy‐related applications and beyond.     

Solution-processed graphene/MnO2 nanostructured textiles for high-performance electrochemical capacitors

Large scale energy storage system with low cost, high power, and long cycle life is crucial for addressing the energy problem when connected with renewable energy production. To realize grid-scale applications of the energy storage devices, there remain several key issues including the development of low-cost, high-performance materials that are environmentally friendly and compatible with low-temperature and large-scale processing. In this report, we demonstrate that solution-exfoliated graphene nanosheets (～5 nm thickness) can be conformably coated from solution on three-dimensional, porous textiles support structures for high loading of active electrode materials and to facilitate the access of electrolytes to those materials. With further controlled electrodeposition of pseudocapacitive MnO(2) nanomaterials, the hybrid graphene/MnO(2)-based textile yields high-capacitance performance with specific capacitance up to 315 F/g achieved. Moreover, we have successfully fabricated asymmetric electrochemical capacitors with graphene/MnO(2)-textile as the positive electrode and single-walled carbon nanotubes (SWNTs)-textile as the negative electrode in an aqueous Na(2)SO(4) electrolyte solution. These devices exhibit promising characteristics with a maximum power density of 110 kW/kg, an energy density of 12.5 Wh/kg, and excellent cycling performance of ～95% capacitance retention over 5000 cycles. Such low-cost, high-performance energy textiles based on solution-processed graphene/MnO(2) hierarchical nanostructures offer great promise in large-scale energy storage device applications.     

Colloidal Nanosurfactants for 3D Conformal Printing of 2D van der Waals Materials

Printing techniques using nanomaterials have emerged as a versatile tool for fast prototyping and potentially large-scale manufacturing of functional devices. Surfactants play a significant role in many printing processes due to their ability to reduce interfacial tension between ink solvents and nanoparticles and thus improve ink colloidal stability. Here, a colloidal graphene quantum dot (GQD)-based nanosurfactant is reported to stabilize various types of 2D materials in aqueous inks. In particular, a graphene ink with superior colloidal stability is demonstrated by GQD nanosurfactants via the π–π stacking interaction, leading to the printing of multiple high-resolution patterns on various substrates using a single printing pass. It is found that nanosurfactants can significantly improve the mechanical stability of the printed graphene films compared with those of conventional molecular surfactant, as evidenced by 100 taping, 100 scratching, and 1000 bending cycles. Additionally, the printed composite film exhibits improved photoconductance using UV light with 400 nm wavelength, arising from excitation across the nanosurfactant bandgap. Taking advantage of the 3D conformal aerosol jet printing technique, a series of UV sensors of heterogeneous structures are directly printed on 2D flat and 3D spherical substrates, demonstrating the potential of manufacturing geometrically versatile devices based on nanosurfactant inks.     

Tuning Solute‐Redistribution Dynamics for Scalable Fabrication of Colloidal Quantum‐Dot Optoelectronics

Solution‐processed colloidal quantum dots (CQDs) are attractive materials for the realization of low‐cost and efficient optoelectronic devices. Although impressive CQD‐solar‐cell performance has been achieved, the fabrication of CQD films is still limited to laboratory‐scale small areas because of the complicated deposition of CQD inks. Large‐area, uniform deposition of lead sulfide (PbS) CQD inks is successfully realized for photovoltaic device applications by engineering the solute redistribution of CQD droplets. It is shown experimentally and theoretically that the solute‐redistribution dynamics of CQD droplets are highly dependent on the movement of the contact line and on the evaporation kinetics of the solvent. By lowering the friction constant of the contact line and increasing the evaporation rate of the droplets, a uniform deposition of CQD ink in length and width over large areas is realized. By utilizing a spray‐coating process, large‐area (up to 100 cm²) CQD films are fabricated with 3–7% thickness variation on various substrates including glass, indium tin oxide glass, and polyethylene terephthalate. Furthermore, scalable fabrication of CQD solar cells is demonstrated with 100 cm² CQD films which exhibits a notably high efficiency of 8.10%.     

Stable and Biocompatible Carbon Nanotube Ink Mediated by Silk Protein for Printed Electronics

Ink-based processes, which enable scalable fabrication of flexible devices based on nanomaterials, are one of the practical approaches for the production of wearable electronics. However, carbon nanotubes (CNTs), which possess great potential for flexible electronics, are facing challenges for use in inks due to their low dispersity in most solvents and suspicious cytotoxicity. Here, a stable and biocompatible CNT ink, which is stabilized by sustainable silk sericin and free from any artificial chemicals, is reported. The ink shows stability up to months, which can be attributed to the formation of sericin–CNT (SSCNT) hybrid through non-covalent interactions. It is demonstrated that the SSCNT ink can be used for fabricating versatile circuits on textile, paper, and plastic films through various techniques. As proofs of concept, electrocardiogram electrodes, breath sensors, and electrochemical sensors for monitoring human health and activity are fabricated, demonstrating the great potential of the SSCNT ink for smart wearables.     

Combined power of perovskites and silicon solar cells

The photovoltaic (PV) or solar cells technology can be categorised into two main groups, the wafer‐based and thin‐film based PVs. The wafer‐based PVs include the commonly known crystalline silicon (c‐Si) and gallium arsenide (GaAs) cells. The GaAs cells exhibit higher efficiency compared to crystalline silicon (c‐Si) cells but it is the later that dominates the commercial market. Thin‐film based (2nd Generation) PVs, including cadmium telluride (CdTe), amorphous silicon (a‐Si:H) and copper‐indium‐gallium‐selenide (CIGS), generally absorb light more efficiently than wafer‐based cells and can allow the use of materials in very thin films form. CdTe PVs have proven to be highly efficient but holds only a few percentage share of the market. There is still a need for more R&D before further commercialisation. An emerging and relatively new class of thin‐film based photovoltaics (3rd Generation) technology that has the potential to overcome the current energy conversion efficiencies and performance by making use of novel materials. This class of PVs include organic photovoltaic (OPV), dye‐synthesised solar cells (DSSC), quantum‐dot (QD) and last but not least, the perovskite PV. Perovskite PVs can offer a low cost energy generation solution with the best device conversion efficiencies have shot from lower than 4% in 2009 to more than 21% in 2016. Perovskite based devices can be fabricated using vacuum thermal evaporation or by solution processing of the active layers. Although most recent perovskite solar cells with record efficiencies (>20%) are prepared via solution processing, the early breakthrough in perovskite solar cells was made with vacuum processed perovskites thin films. Vacuum thermal evaporation offers the ability and flexibility to prepare solar cell devices in various configuration. Recent developments in the field of perovskite demonstrates its compatibility with both, first and second generation PV technologies, and is therefore likely to be embraced by the conventional PV industry and make its way into utility‐scale power generation.     

Gigahertz Electromagnetic Structures via Direct Ink Writing for Radio‐Frequency Oscillator and Transmitter Applications

Radio‐frequency (RF) electronics, which combine passive electromagnetic devices and active transistors to generate and process gigahertz (GHz) signals, provide a critical basis of ever‐pervasive wireless networks. While transistors are best realized by top‐down fabrication, relatively larger electromagnetic passives are within the reach of printing techniques. Here, direct writing of viscoelastic silver‐nanoparticle inks is used to produce a broad array of RF passives operating up to 45 GHz. These include lumped devices such as inductors and capacitors, and wave‐based devices such as transmission lines, their resonant networks, and antennas. Moreover, to demonstrate the utility of these printed RF passive structures in active RF electronic circuits, they are combined with discrete transistors to fabricate GHz self‐sustained oscillators and synchronized oscillator arrays that provide RF references, and wireless transmitters clocked by the oscillators. This work demonstrates the synergy of direct ink writing and RF electronics for wireless applications.     

Carbon‐Based Microbial‐Fuel‐Cell Electrodes: From Conductive Supports to Active Catalysts

Microbial fuel cells (MFCs) have attracted considerable interest due to their potential in renewable electrical power generation using the broad diversity of biomass and organic substrates. However, the difficulties in achieving high power densities and commercially affordable electrode materials have limited their industrial applications to date. Carbon materials, which can exhibit a wide range of different morphologies and structures, usually possess physiological activity to interact with microorganisms and are therefore fast‐emerging electrode materials. As the anode, carbon materials can significantly promote interfacial microbial colonization and accelerate the formation of extracellular biofilms, which eventually promotes the electrical power density by providing a conductive microenvironment for extracellular electron transfer. As the cathode, carbon‐based materials can function as catalysts for the oxygen‐reduction reaction, showing satisfying activities and efficiencies nowadays even reaching the performance of Pt catalysts. Here, first, recent advancements on the design of carbon materials for anodes in MFCs are summarized, and the influence of structure and surface functionalization of different types of carbon materials on microorganism immobilization and electrochemical performance is elucidated. Then, synthetic strategies and structures of typical carbon‐based cathodes in MFCs are briefly presented. Furthermore, future applications of carbon‐electrode‐based MFC devices in the energy, environmental, and biological fields are discussed, and the emerging challenges in transferring them from laboratory to industrial scale are described.     

1D Carbon‐Based Nanocomposites for Electrochemical Energy Storage

Electrochemical energy storage (EES) devices have attracted immense research interests as an effective technology for utilizing renewable energy. 1D carbon‐based nanostructures are recognized as highly promising materials for EES application, combining the advantages of functional 1D nanostructures and carbon nanomaterials. Here, the recent advances of 1D carbon‐based nanomaterials for electrochemical storage devices are considered. First, the different categories of 1D carbon‐based nanocomposites, namely, 1D carbon‐embedded, carbon‐coated, carbon‐encapsulated, and carbon‐supported nanostructures, and the different synthesis methods are described. Next, the practical applications and optimization effects in electrochemical energy storage devices including Li‐ion batteries, Na‐ion batteries, Li–S batteries, and supercapacitors are presented. After that, the advanced in situ detection techniques that can be used to investigate the fundamental mechanisms and predict optimization of 1D carbon‐based nanocomposites are discussed. Finally, an outlook for the development trend of 1D carbon‐based nanocomposites for EES is provided.