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.     

Recent Advances on High-Entropy Alloys for 3D Printing

Boosted by the success of high-entropy alloys (HEAs) manufactured by conventional processes in various applications, the development of HEAs for 3D printing has been advancing rapidly in recent years. 3D printing of HEAs gives rise to a great potential for manufacturing geometrically complex HEA products with desirable performances, thereby inspiring their increased appearance in industrial applications. Herein, a comprehensive review of the recent achievements of 3D printing of HEAs is provided, in the aspects of their powder development, printing processes, microstructures, properties, and potential applications. It begins with the introduction of the fundamentals of 3D printing and HEAs, as well as the unique properties of 3D-printed HEA products. The processes for the development of HEA powders, including atomization and mechanical alloying, and the powder properties, are then presented. Thereafter, typical processes for printing HEA products from powders, namely, directed energy deposition, selective laser melting, and electron beam melting, are discussed with regard to the phases, crystal features, mechanical properties, functionalities, and potential applications of these products (particularly in the aerospace, energy, molding, and tooling industries). Finally, perspectives are outlined to provide guidance for future research.     

High‐Performance Materials for 3D Printing in Chemical Synthesis Applications

3D printing has emerged as an enabling technology for miniaturization. High‐precision printing techniques such as stereolithography are capable of printing microreactors and lab‐on‐a‐chip devices for efficient parallelization of biological and biochemical reactions under reduced uptake of reactants. In the world of chemistry, however, up until now, miniaturization has played a minor role. The chemical and thermal stability of regular 3D printing resins is insufficient for sustaining the harsh conditions of chemical reactions. Novel material formulations that produce highly stable 3D‐printed chips are highly sought for bringing chemistry up‐to‐date on the development of miniaturization. In this work, a brief review of recent developments in highly stable materials for 3D printing is given. This work focuses on three highly stable 3D‐printable material systems: transparent silicate glasses, ceramics, and fluorinated polymers. It is further demonstrated that 3D printing is also a versatile technique for surface structuring of polymers to enhance their wetting performance. Such micro/nanostructuring is key to selectively wetting surface patterns that are versatile for chemical arrays and droplet synthesis.     

3D Printing of Ceramics with Controllable Green-Body Configuration Assisted by the Polyvinyl Alcohol-Based Physical Gels

Additive manufacturing of ceramics has received intense attention. In particular, 3D-printed ceramics with customized shapes are highly desirable in the chemical industry, aerospace, and biomedical engineering. Nevertheless, developing a simple and cost-effective process that shapes dense ceramics to complex geometries remains challenging because of the high hardness and low ductility of ceramic materials. Extrusion-based printing, such as direct ink writing (DIW), often requires supporting materials that pose additional difficulties during printing. Herein, a simple approach is developed to produce stretchable ceramic green bodies of zirconia and alumina for DIW. The ink is composed of polyvinyl alcohol (PVA) and an aqueous suspension of ceramic powders. Besides the colloidal network formed by the ceramic particles, PVA plays an important role in tuning the printability of the aqueous ink. Through a freeze-thaw process, PVA crystallizes to form physical networks. This strategy provides highly stretchable hydrogel green bodies that can be reprogrammed to complex geometries difficult for common DIW printing. The subsequent drying, debinding, and sintering processes produce ceramics with dense structures and fine mechanical properties. In short, this work demonstrates an efficient method for the DIW of ceramic parts that can be reprogrammed to complex geometries.     

Evolution of 3D Printing Methods and Materials for Electrochemical Energy Storage

Additive manufacturing has revolutionized the building of materials, and 3D-printing has become a useful tool for complex electrode assembly for batteries and supercapacitors. The field initially grew from extrusion-based methods and quickly evolved to photopolymerization printing, while supercapacitor technologies less sensitive to solvents more often involved material jetting processes. The need to develop higher-resolution multimaterial printers is borne out in the performance data of recent 3D printed electrochemical energy storage devices. Underpinning every part of a 3D-printable battery are the printing method and the feed material. These influence material purity, printing fidelity, accuracy, complexity, and the ability to form conductive, ceramic, or solvent-stable materials. The future of 3D-printable batteries and electrochemical energy storage devices is reliant on materials and printing methods that are co-operatively informed by device design. Herein, the material and method requirements in 3D-printable batteries and supercapacitors are addressed and requirements for the future of the field are outlined by linking existing performance limitations to requirements for printable energy-storage materials, casings, and direct printing of electrodes and electrolytes. A guide to materials and printing method choice best suited for alternative-form-factor energy-storage devices to be designed and integrated into the devices they power is thus provided.     

3‐D Printing and Development of Fluoropolymer Based Reactive Inks

Engineering reactive materials is an ever present goal in the energetics community. The desire is to have energetics configured in such a manner that performance is tailored and energy delivery can be targeted. Additive manufacturing (3‐D printing) is one area that could significantly improve our capabilities in this area, if adequate formulations are developed. In this paper, fluoropolymer based reactive inks are developed with micron (mAl) and nanoscale aluminum (nAl) serving, as the fuel at high solids loading (up to 67 wt%) and their viscosity required for 3‐D printing is detailed. For the pen‐type technique and valves used in this work, it is required to have viscosities on the order of 10⁴–10⁵ cP. For printed traces with apparent diameters under <500 μm, the combustion velocities for both micron and nano scale aluminum formulations, are approximately identical: 30 ± 3 versus 32 ± 2 mm s^?1, respectively. Further increasing the apparent diameter is shown to increase the combustion velocity in the case of the nanoscale aluminum formulation by four‐fold over that of the micron scale aluminum formulation, but it plateaus as it approaches an apparent diameter of 2 mm. The results suggest with proper architecture that tailorable combustion rates and energy delivery are feasible.

     

Extrusion‐Based 3D Printing of Hierarchically Porous Advanced Battery Electrodes

A highly porous 2D nanomaterial, holey graphene oxide (hGO), is synthesized directly from holey graphene powder and employed to create an aqueous 3D printable ink without the use of additives or binders. Stable dispersions of hydrophilic hGO sheets in water (≈100 mg mL^?1) can be readily achieved. The shear‐thinning behavior of the aqueous hGO ink enables extrusion‐based printing of fine filaments into complex 3D architectures, such as stacked mesh structures, on arbitrary substrates. The freestanding 3D printed hGO meshes exhibit trimodal porosity: nanoscale (4–25 nm through‐holes on hGO sheets), microscale (tens of micrometer‐sized pores introduced by lyophilization), and macroscale (<500 µm square pores of the mesh design), which are advantageous for high‐performance energy storage devices that rely on interfacial reactions to promote full active‐site utilization. To elucidate the benefit of (nano)porosity and structurally conscious designs, the additive‐free architectures are demonstrated as the first 3D printed lithium–oxygen (Li–O₂) cathodes and characterized alongside 3D printed GO‐based materials without nanoporosity as well as nanoporous 2D vacuum filtrated films. The results indicate the synergistic effect between 2D nanomaterials, hierarchical porosity, and overall structural design, as well as the promise of a freeform generation of high‐energy‐density battery systems.     

3D打印主要成形工艺及其应用进展

3D打印是以计算机图形数据为基础,通过逐层堆积的方式构建实体,具有高柔性制造以及对复杂零件自由快速成形的特点.从文献研究入手,重点介绍了光固化成形、熔融沉积制造、选区激光烧结、选区激光熔化、三维印刷成形、分层实体制造等典型3D打印工艺的成形原理以及研究进展,在此基础上着重概述了3D打印在生物医学、航空航天、建筑工程领域的应用.简要分析了当前3D打印技术发展中存在的一些问题并提出了一系列解决方案.3D打印技术的出现,给传统制造技术带来了革命性改变,其应用范围广泛,未来一定会融入到人们生活的方方面面.     

3D‐Printing Electrolytes for Solid‐State Batteries

Solid‐state batteries have many enticing advantages in terms of safety and stability, but the solid electrolytes upon which these batteries are based typically lead to high cell resistance. Both components of the resistance (interfacial, due to poor contact with electrolytes, and bulk, due to a thick electrolyte) are a result of the rudimentary manufacturing capabilities that exist for solid‐state electrolytes. In general, solid electrolytes are studied as flat pellets with planar interfaces, which minimizes interfacial contact area. Here, multiple ink formulations are developed that enable 3D printing of unique solid electrolyte microstructures with varying properties. These inks are used to 3D‐print a variety of patterns, which are then sintered to reveal thin, nonplanar, intricate architectures composed only of Li₇La₃Zr₂O₁₂ solid electrolyte. Using these 3D‐printing ink formulations to further study and optimize electrolyte structure could lead to solid‐state batteries with dramatically lower full cell resistance and higher energy and power density. In addition, the reported ink compositions could be used as a model recipe for other solid electrolyte or ceramic inks, perhaps enabling 3D printing in related fields.     

Advances in Polyimide‐Based Materials for Space Applications

The space environment raises many challenges for new materials development and ground characterization. These environmental hazards in space include solar radiation, energetic particles, vacuum, micrometeoroids and debris, and space plasma. In low Earth orbits, there is also a significant concentration of highly reactive atomic oxygen (AO). This Progress Report focuses on the development of space‐durable polyimide (PI)‐based materials and nanocomposites and their testing under simulated space environment. Commercial PIs suffer from AO‐induced erosion and surface electric charging. Modified PIs and PI‐based nanocomposites are developed and tested to resist degradation in space. The durability of PIs in AO is successfully increased by addition of polyhedral oligomeric silsesquioxane. Conductive materials are prepared based on composites of PI and either carbon nanotube (CNT) sheets or 3D‐graphene structures. 3D PI structures, which can expand PI space applications, made by either additive manufacturing (AM) or thermoforming, are presented. The selection of AM‐processable engineering polymers in general, and PIs in particular, is relatively limited. Here, innovative preliminary results of a PI‐based material processed by the PolyJet technology are presented.     

粉末钛合金3D打印技术研究进展

粉末钛合金3D打印技术以低成本、易成形、柔性化制备、零件性能优异等优势,近年来成为钛合金近净成形制造领域的研究热点。总结了国内外粉末钛合金3D打印技术的研究进展,包括激光熔化沉积成形技术(LMD)、激光选区熔化成形技术(SLM)、电子束选区熔化成形技术(SEBM)。比较研究了3种成形技术制备的钛合金的组织特点及力学性能,并讨论了粉末钛合金3D打印技术的市场化现状与未来发展趋势。     

3D打印技术对产品的影响

目的研究3D打印技术性因素对产品从内在概念到外在结构与形式的影响,科学地认知该技术在设计方面的价值。重点研究在3D打印技术背景下产品属性及价值、生产与制造、设计、结构与形态等诸方面呈现出新的变化趋势。方法通过对"商品"与"产品"概念变迁的阐述,揭示3D打印技术影响下产品价值与内涵的变迁形式。分析3D打印技术对产品生产制造、造型与结构等方面的影响,进一步理清3D打印技术对产品、产品设计与生产、产品结构与形态等方面影响的形式与程度。结论 3D打印技术在设计范畴、设计观念、设计核心问题等方面突破了传统的设计认知藩篱。通过梳理新技术对产品多方面的影响,从而建立起新技术背景下的设计认知,以实现技术价值与创新设计价值的进一步融合。     

Recent Advances in Enabling Technologies in 3D Printing for Precision Medicine

Advances in areas such as data analytics, genomics, and imaging have revealed individual patient complexities and exposed the inherent limitations of generic therapies for patient treatment. These observations have also fueled the development of precision medicine approaches, where therapies are tailored for the individual rather than the broad patient population. 3D printing is a field that intersects with precision medicine through the design of precision implants with patient-directed shapes, structures, and materials or for the development of patient-specific in vitro models that can be used for screening precision therapeutics. Toward their success, advances in 3D printing and biofabrication technologies are needed with enhanced resolution, complexity, reproducibility, and speed and that encompass a broad range of cells and materials. The overall goal of this progress report is to highlight recent advances in 3D printing technologies that are helping to enable advances important in precision medicine.     

3D Printing of Salt as a Template for Magnesium with Structured Porosity

Porosity is an essential feature in a wide range of applications that combine light weight with high surface area and tunable density. Porous materials can be easily prepared with a vast variety of chemistries using the salt‐leaching technique. However, this templating approach has so far been limited to the fabrication of structures with random porosity and relatively simple macroscopic shapes. Here, a technique is reported that combines the ease of salt leaching with the complex shaping possibilities given by additive manufacturing (AM). By tuning the composition of surfactant and solvent, the salt‐based paste is rheologically engineered and printed via direct ink writing into grid‐like structures displaying structured pores that span from the sub‐millimeter to the macroscopic scale. As a proof of concept, dried and sintered NaCl templates are infiltrated with magnesium (Mg), which is typically highly challenging to process by conventional AM techniques due to its highly oxidative nature and high vapor pressure. Mg scaffolds with well‐controlled, ordered porosity are obtained after salt removal. The tunable mechanical properties and the potential to be predictably bioresorbed by the human body make these Mg scaffolds attractive for biomedical implants and demonstrate the great potential of this additive technique.