Additive manufacturing for energy storage: Methods,designs and material selection for customizable 3D printed batteries and supercapacitors

Additive manufacturing and 3D printing in particular have the potential to revolutionize existing fabrication processes, where objects with complex structures and shapes can be built with multifunctional material systems. For electrochemical energy storage devices such as batteries and supercapacitors, 3D printing methods allows alternative form factors to be conceived based on the end use application need in mind at the design stage. Additively manufactured energy storage devices require active materials and composites that are printable, and this is influenced by performance requirements and the basic electrochemistry. The interplay between electrochemical response, stability, material type, object complexity and end use application are key to realising 3D printing for electrochemical energy storage. Here, we summarise recent advances and highlight the important role of methods, designs and material selection for energy storage devices made by 3D printing, which is general to the majority of methods in use currently.     

Polymer 4D printing: Advanced shape-change and beyond

4D printing is an exciting branch of additive manufacturing. It relies on established 3D printing techniques to fabricate objects in much the same way. However, structures which fall into the 4D printed category have the ability to change with time, hence the “extra dimension.” The common perception of 4D printed objects is that of macroscopic single-material structures limited to point-to-point shape change only, in response to either heat or water. However, in the area of polymer 4D printing, recent advancements challenge this understanding. A host of new polymeric materials have been designed which display a variety of wonderful effects brought about by unconventional stimuli, and advanced additive manufacturing techniques have been developed to accommodate them. As a result, the horizons of polymer 4D printing have been broadened beyond what was initially thought possible. In this review, we showcase the many studies which evolve the very definition of polymer 4D printing, and reveal emerging areas of research integral to its advancement.     

PolyChemPrint: A hardware and software framework for benchtop additive manufacturing of functional polymeric materials

Additive manufacturing (AM, 3D Printing) of hierarchical polymer structures for a targeted function represents a grand challenge in the field of polymer science and engineering. Because advanced functional materials often do not possess suitable mechanical and rheological properties for conventional fused deposition modeling, a key challenge that researchers face is in integrating custom deposition tool heads that enable printing of non-filamentary materials while preserving synchrony with the motion axes. In this article, we demonstrate a highly versatile hardware and software platform for melt and solution-phase benchtop AM and highlight patterning and post-deposition processing of a series of non-filament forming functional polymers, including PS-b-PLA bottlebrush block copolymers, semiconducting polymer DPP2T-TT, conducting polymer PEDOT:PSS [poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)], and an SiO₂-PE nanoporous polymer matrix composite. We present a free and open-source Python module, PolyChemPrint, which serves as a research-optimized AM control software. The cross-platform (Windows/Linux) software is designed to be extremely flexible in terms the hardware that can be connected and a detailed user manual and developer guide are provided for use by researchers without extensive computer programming experience. Finally, we provide extensive details of the hardware used for operation of low- and high-pressure pneumatic extruders and a laser module as rapidly interchangeable tool heads.     

Thermoplastic Cellulose-Based Compound for Additive Manufacturing

The increasing environmental awareness is driving towards novel sustainable high-performance materials applicable for future manufacturing technologies like additive manufacturing (AM). Cellulose is abundantly available renewable and sustainable raw material. This work focused on studying the properties of thermoplastic cellulose-based composites and their properties using injection molding and 3D printing of granules. The aim was to maximize the cellulose content in composites. Different compounds were prepared using cellulose acetate propionate (CAP) and commercial cellulose acetate propionate with plasticizer (CP) as polymer matrices, microcellulose (mc) and novel cellulose-ester additives; cellulose octanoate (C8) and cellulose palmitate (C16). The performance of compounds was compared to a commercial poly(lactic acid)-based cellulose fiber containing composite. As a result, CP-based compounds had tensile and Charpy impact strength properties comparable to commercial reference, but lower modulus. CP-compounds showed glass transition temperature (Tg) over 58% and heat distortion temperature (HDT) 12% higher compared to reference. CAP with C16 had HDT 82.1 °C. All the compounds were 3D printable using granular printing, but CAP compounds had challenges with printed layer adhesion. This study shows the potential to tailor thermoplastic cellulose-based composite materials, although more research is needed before obtaining all-cellulose 3D printable composite material with high-performance.     

It's in the Fine Print: Erasable Three‐Dimensional Laser‐Printed Micro‐ and Nanostructures

3D printing, on all scales, is currently a vibrant topic in scientific and industrial research as it has enormous potential to radically change manufacturing. Owing to the inherent nature of the manufacturing process, 3D printed structures may require additional material to structurally support complex features. Such support material must be removed after printing—sometimes termed subtractive manufacturing—without adversely affecting the remaining structure. An elegant solution is the use of photoresists containing labile bonds that allow for controlled cleavage with specific triggers. Herein, we explore state‐of‐the‐art cleavable photoresists for 3D direct laser writing, as well as their potential to combine additive and subtractive manufacturing in a hybrid technology. We discuss photoresist design, feature resolution, cleavage properties, and current limitations of selected examples. Furthermore, we share our perspective on possible labile bonds, and their corresponding cleavage trigger, which we believe will have a critical impact on future applications and expand the toolbox of available cleavable photoresists.     

3D打印生物医用材料研究进展

3D打印(亦称增材制造)技术因其独特的材料成型优势,在组织工程、航空航天、汽车制造、以及电子工业等众多领域显示出巨大的应用潜力。然而,在实际生物医学应用中,3D打印生物器件和组织器官除了要求具有复杂的结构和优异的生物学性能外,其打印结构的表面性质也需满足某些特定的要求,如3D打印组织骨架和器官必须具有生物相容性、抗菌性及细胞粘附性等。因此,将3D打印与传统表面修饰技术相结合,在不改变材料三维结构的基础上调控其表面生物化学性质,从而赋予3D打印生物骨架器官多功能化,可实现更为广泛的应用。本文以3D打印生物骨架及器官的表面修饰为主要内容对就近年来3D打印生物医用材料的最新研究进展进行了综述。     

3D Printing of Silk Protein Structures by Aqueous Solvent‐Directed Molecular Assembly

Hierarchical molecular assembly is a fundamental strategy for manufacturing protein structures in nature. However, to translate this natural strategy into advanced digital manufacturing like three‐dimensional (3D) printing remains a technical challenge. This work presents a 3D printing technique with silk fibroin to address this challenge, by rationally designing an aqueous salt bath capable of directing the hierarchical assembly of the protein molecules. This technique, conducted under aqueous and ambient conditions, results in 3D proteinaceous architectures characterized by intrinsic biocompatibility/biodegradability and robust mechanical features. The versatility of this method is shown in a diversity of 3D shapes and a range of functional components integrated into the 3D prints. The manufacturing capability is exemplified by the single‐step construction of perfusable microfluidic chips which eliminates the use of supporting or sacrificial materials. The 3D shaping capability of the protein material can benefit a multitude of biomedical devices, from drug delivery to surgical implants to tissue scaffolds. This work also provides insights into the recapitulation of solvent‐directed hierarchical molecular assembly for artificial manufacturing.     

Hierarchical Co‐Assembly Enhanced Direct Ink Writing

Integrating intelligent molecular systems into 3D printing materials and transforming their molecular functions to the macroscale with controlled superstructures will unleash great potential for the development of smart materials. Compared to macromolecular 3D printing materials, self‐assembled small‐molecule‐based 3D printing materials are very rare owing to the difficulties of facilitating 3D printability as well as preserving their molecular functions macroscopically. Herein, we report a general approach for the integration of functional small molecules into 3D printing materials for direct ink writing through the introduction of a supramolecular template. A variety of inorganic and organic small‐molecule‐based inks were 3D‐printed, and their superstructures were refined by post‐printing hierarchical co‐assembly. Through spatial and temporal control of individual molecular events from the nano‐ to the macroscale, fine‐tuned macroscale features were successfully installed in the monoliths.     

4D Bioprinting: Technological Advances in Biofabrication

The development of the three‐dimensional (3D) printer has resulted in significant advances in a number of fields, including rapid prototyping and biomedical devices. For 3D structures, the inclusion of dynamic responses to stimuli is added to develop the concept of four‐dimensional (4D) printing. Typically, 4D printing is useful for biofabrication by reproducing a stimulus‐responsive dynamic environment corresponding to physiological activities. Such a dynamic environment can be precisely designed with an understanding of shape‐morphing effects (SMEs), which enables mimicking the functionality or intricate geometry of tissues. Here, 4D bioprinting is investigated for clinical use, for example, in drug delivery systems, tissue engineering, and surgery in vivo. This review presents the concept of 4D bioprinting and smart materials defined by SMEs and stimulus‐responsive mechanisms. Then, biomedical smart materials and applications are discussed along with future perspectives.     

3D printing of conjugated polymers

Three‐dimensional (3D) printing brings exciting prospects to the realm of conjugated polymers (CPs) and organic electronics through vastly enhanced design flexibility, structural complexity, and environmental sustainability. However, the use of 3D printing for CPs is still in its infancy and remains full of challenges. In this review, we highlight recent studies that demonstrate proof‐of‐concept strategies to mitigate some of these problems. Two general additive manufacturing approaches are featured: direct ink writing and vat photopolymerization. We conclude with an outlook for this thriving field of research and draw attention to the new possibilities that 3D printing can bring to CPs. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1592–1605     

Additive manufacturing of fire‐retardant ethylene‐vinyl acetate

Thermocompression (with also extrusion and injection molding) is a classical polymer shaping manufacturing, but it does not easily allow designing sophisticated shapes without using a complex mold, on the contrary to 3D printing (or polymer additive manufacturing), which is a very flexible technique. Among all 3D printing techniques, fused deposition modeling is of high potential for product manufacturing, with the capability to compete with conventional polymer processing techniques. This is a quite low cost 3D printing technique, but the range of filaments commercially available is limited. However, in some specific 3D printing processes, no filaments are necessary. Polymers pellets feed directly the printing nozzle allowing to investigate many polymeric matrices with no commercial limitation. This is of high interest for the design of flame‐retarded materials, but literature is scarce in that field. In this paper, a comparison between thermocompression and 3D printing processes was performed on both neat ethylene‐vinyl acetate (EVA) copolymer and EVA flame retarded with aluminum triHydroxyde (ATH) containing different loadings (30 or 65 wt%) and with expandable graphite (EG), ie, EVA/ATH (30 wt%), EVA/ATH (65 wt%), and EVA/EG (10 wt%), respectively. Morphological comparisons, using microscopic and electronic microprobe analyses, revealed that 3D printed plates have lower apparent density and higher porosity than thermocompressed plate. The fire‐retardant properties of thermocompressed and 3D printed plates were then evaluated using mass loss calorimeter test at 50 kW/m². Results highlight that 3D printing can be used to produce flame‐retardant systems. This work is a pioneer study exploring the feasibility of using polymer additive manufacturing technology for designing efficient flame‐retarded materials.     

Inkjet Printing of 2D Layered Materials

Inkjet printing of 2D layered materials, such as graphene and MoS₂, has attracted great interests for emerging electronics. However, incompatible rheology, low concentration, severe aggregation and toxicity of solvents constitute critical challenges which hamper the manufacturing efficiency and product quality. Here, we introduce a simple and general technology concept (distillation‐assisted solvent exchange) to efficiently overcome these challenges. By implementing the concept, we have demonstrated excellent jetting performance, ideal printing patterns and a variety of promising applications for inkjet printing of 2D layered materials.     

Synthesis and characterization of acrylamide/acrylic acid hydrogels crosslinked using a novel diacrylate of glycerol to produce multistructured materials

In this work we propose a new crosslinking agent and the method to use it for the synthesis of acrylate based hydrogels. The use of this diacrylate of glycerol, synthesized in our laboratory, allows the generation of materials with well defined micro‐structures in the dry state, unique meso‐ and macro‐structures during swelling, and enhanced mechanical properties and swelling capacity in water. These properties depend on the crosslinking agent concentration, as well as synthesis thermal history. Poly(acrylamide‐co‐acrylic acid) hydrogels are commonly crosslinked with N, N′‐methylenebisacrylamide or N‐isopropylacrylamide. Here we obtain and use a new crosslinking agent, obtained from the reaction between glycerol and acrylic acid to produce a Diacrylate of glycerol (DAG). Two synthesis methods at equivalent molar ratio of acrylamide/acrylic acid (AM/AA) were analyzed. The mechanical properties, the swelling capacity, and the morphology at microscale of these hydrogels showed a well defined transition at a critical concentration of crosslinking agent. DAG induces the generation of hydrogels with hierarchichal structure. The micro‐structure surface morphology was investigated by scanning electron microscopy, the meso‐structure by polarized light microscopy and the macro‐structure by CCD imaging. The hydrogels with hierarchical structures showed improved mechanical properties when compared with structureless hydrogels. Control of the microstructure allows the generation of materials for different applications, i.e. templates or smart materials that interact with electromagnetic radiation. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2667–2679, 2008     

Fused deposition modeling-based additive manufacturing (3D printing): techniques for polymer material systems

While the developments of additive manufacturing (AM) techniques have been remarkable thus far, they are still significantly limited by the range of printable, functional material systems that meet the requirements of a broad range of industries; including the health care, manufacturing, packaging, aerospace, and automotive industries. Furthermore, with the rising demand for sustainable developments, this review broadly gives the reader a good overview of existing AM techniques; with more focus on the extrusion-based technologies (fused deposition modeling and direct ink writing) due to their scalability, cost efficiency and wider range of material processability. It then goes on to identify the innovative materials and recent research activities that may support the sustainable development of extrusion-based techniques for functional and multifunctional (4D printing) part and product fabrication.     

Three-dimensionally printed electrochemical systems for biomedical analytical applications

Additive manufacturing (3D-printing) has revolutionized many areas of the manufacturing. Three-dimensional printing offers enormous potential to biomedical devices, including electroanalytical systems. The motivation for 3D printing is rapid prototyping and decentralized customizable fabrication of bioanalytical systems in the diverse and remote areas of the globe. We overview the recent trends and discuss the fabrication and applications of 3D printed polymer/carbon and metal electrodes and whole electrochemical systems for biomedical applications and DNA detection. We show that sky is the limit and envision whole analytical systems, including electronics, to be 3D printed in the future for diagnostics in the remote areas of the globe.     

Advanced Polymer Designs for Direct-Ink-Write 3D Printing

The rapid development of additive manufacturing techniques, also known as three-dimensional (3D) printing, is driving innovations in polymer chemistry, materials science, and engineering. Among current 3D printing techniques, direct ink writing (DIW) employs viscoelastic materials as inks, which are capable of constructing sophisticated 3D architectures at ambient conditions. In this perspective, polymer designs that meet the rheological requirements for direct ink writing are outlined and successful examples are summarized, which include the development of polymer micelles, co-assembled hydrogels, supramolecularly cross-linked systems, polymer liquids with microcrystalline domains, and hydrogels with dynamic covalent cross-links. Furthermore, advanced polymer designs that reinforce the mechanical properties of these 3D printing materials, as well as the integration of functional moieties to these materials are discussed to inspire new polymer designs for direct ink writing and broadly 3D printing.     

Multifaceted polymeric materials in three‐dimensional processing (3DP) technologies: Current progress and prospects

Three‐dimensional printing (3DP) technologies, which are sets of powerful deposition methods employed to fabricate 3D objects with materials in the fields of material sciences and engineering, biomedical and biocompatible structural components, automotive, aviation, and polymers, among others, are currently rapidly developing manufacturing technologies. The methods have significant advantages, which include designing flexibility, enhanced geometrical freedom, low cost, and net shape manufacture, among others, over the traditional “subtractive” method. This review highlights the major 3D printing techniques, especially in the fields of advanced polymeric material fabrication and engineering, as well as the synergy in the incorporation of different types of polymeric materials and composites in a process that will lead to an enhancement of dimensional accuracy for 3D technologies. Furthermore, composite ink systems especially polymer‐based and hydrogel‐based in tissue engineering applications are also discussed.     

Dimensional considerations on the mechanical properties of 3D printed polymer parts

Additive manufacturing offers a useful and accessible tool for prototyping and manufacturing small volume functional parts. Polylactic acid (PLA) and thermoplastic polyurethane (TPU) are amongst the most commonly used materials. Characterising 3D printed PLA and TPU is potentially important for both designing and finite element modelling of functional parts. This work explores the mechanical properties of additively manufactured PLA/TPU specimens with consideration to design parameters including size, and infill percentage. PLA/TPU specimens are 3D-printed in selected ISO standard geometries with 20%, 60%, 100% infill percentage. Tensile and compression test results suggest that traditional ISO testing standards might be insufficient in characterising 3D printed materials for finite element modelling or application purposes. Infill percentage in combination to design size, may significantly affect the mechanical performance of 3D printed parts. Dimensional variation may cause inhomogeneity in mechanical properties between large and small cross section areas of the same part. The effect was reduced in small cross section parts where reducing the nominal infill had less effect on the resulting specimens. The results suggest that for 3D printed functional parts with significant dimensional differences between sections, the material properties are not necessarily homogeneous. This consideration may be significant for designers using 3D printing for applications, which include mechanical loading.     

3D printing to innovate biopolymer materials for demanding applications: A review

Biopolymers are widely available, low-/nontoxic, biodegradable, biocompatible, chemically versatile, and inherently functional, making them highly potential for a broad range of applications such as biomedicine, food, textile, and cosmetics. 3D printing (3DP) is capable of fabricating some customized, complex material structures composed of single or multiple material constituents that cannot be achieved by conventional methodologies (e.g. internal structures design); thus, 3DP can greatly expand the application of biopolymer materials. This review presents a comprehensive survey of the latest literature in 3DP technology for materials from biopolymers such as polysaccharides and proteins. The most commonly used 3DP techniques (i.e. inkjet printing, extrusion-based printing, stereolithography, selective laser sintering, and binder jetting) in biomedical and food fields are discussed. Critical factors affecting the quality and accuracy of 3D-printed constructs, including rheological characteristics, printing parameters (e.g. printing rate, and nozzle diameter, movement rate, and height), and post-printing processes (e.g. baking, drying, and crosslinking) are analyzed. The properties and the emerging applications of 3D-printed biopolymer materials in biomedical, food, and even wider applications (e.g. wastewater treatment and sensing) are summarized and evaluated. Finally, challenges and future perspectives are discussed. This review can provide insights into the development of new biopolymer-based inks and new biopolymer-based 3D-printed materials with enhanced properties and functionality.