Inertially enhanced mass transport using 3D-printed porous flow-through electrodes with periodic lattice structures.

Electrochemical reactors utilizing flow-through electrodes (FTEs) provide an attractive path toward the efficient utilization of electrical energy, but their commercial viability and ultimate adoption hinge on attaining high currents to drive productivity and cost competitiveness. Conventional FTEs composed of random, porous media provide limited opportunity for architectural control and engineering of microscale transport. Alternatively, the design freedom engendered by additively manufacturing FTEs yields additional opportunities to further drive performance via flow engineering. Through experiment and validated continuum computation we analyze the mass transfer in three-dimensional (3D)-printed porous FTEs with periodic lattice structures and show that, in contrast to conventional electrodes, the mesoscopic length scales in 3D-printed electrodes lead to an increase in the mass correlation exponent as inertial flow effects dominate. The inertially enhanced mass transport yields mass transfer coefficients that exceed previously reported 3D-printed FTEs by 10 to 100 times, bringing 3D-printed FTE performance on par with conventional materials.

Printing Porous Carbon Aerogels for Low Temperature Supercapacitors.

Maintaining fast charging capability at low temperatures represents a significant challenge for supercapacitors. The performance of conventional porous carbon electrodes often deteriorates quickly with the decrease of temperature due to sluggish ion and charge transport. Here we fabricate a 3D-printed multiscale porous carbon aerogel (3D-MCA) via a unique combination of chemical methods and the direct ink writing technique. 3D-MCA has an open porous structure with a large surface area of ∼1750 m2 g-1. At -70 °C, the symmetric device achieves outstanding capacitance of 148.6 F g-1 at 5 mV s-1. Significantly, it retains a capacitance of 71.4 F g-1 at a high scan rate of 200 mV s-1, which is 6.5 times higher than the non-3D printed MCA. These values rank among the best results reported for low temperature supercapacitors. These impressive results highlight the essential role of open porous structures for preserving capacitive performance at ultralow temperatures.

Retraction: Graded bandgap perovskite solar cells.

This corrects the article DOI: 10.1038/nmat4795.

Graded bandgap perovskite solar cells.

Organic-inorganic halide perovskite materials have emerged as attractive alternatives to conventional solar cell building blocks. Their high light absorption coefficients and long diffusion lengths suggest high power conversion efficiencies, and indeed perovskite-based single bandgap and tandem solar cell designs have yielded impressive performances. One approach to further enhance solar spectrum utilization is the graded bandgap, but this has not been previously achieved for perovskites. In this study, we demonstrate graded bandgap perovskite solar cells with steady-state conversion efficiencies averaging 18.4%, with a best of 21.7%, all without reflective coatings. An analysis of the experimental data yields high fill factors of ∼75% and high short-circuit current densities up to 42.1 mA cm-2. The cells are based on an architecture of two perovskite layers (CH3NH3SnI3 and CH3NH3PbI3-xBrx), incorporating GaN, monolayer hexagonal boron nitride, and graphene aerogel.

Ultralight Conductive Silver Nanowire Aerogels.

Low-density metal foams have many potential applications in electronics, energy storage, catalytic supports, fuel cells, sensors, and medical devices. Here, we report a new method for fabricating ultralight, conductive silver aerogel monoliths with predictable densities using silver nanowires. Silver nanowire building blocks were prepared by polyol synthesis and purified by selective precipitation. Silver aerogels were produced by freeze-casting nanowire aqueous suspensions followed by thermal sintering to weld the nanowire junctions. As-prepared silver aerogels have unique anisotropic microporous structures, with density precisely controlled by the nanowire concentration, down to 4.8 mg/cm3 and an electrical conductivity up to 51 000 S/m. Mechanical studies show that silver nanowire aerogels exhibit "elastic stiffening" behavior with a Young's modulus up to 16 800 Pa.

Supercapacitors Based on Three-Dimensional Hierarchical Graphene Aerogels with Periodic Macropores.

Graphene is an atomically thin, two-dimensional (2D) carbon material that offers a unique combination of low density, exceptional mechanical properties, thermal stability, large surface area, and excellent electrical conductivity. Recent progress has resulted in macro-assemblies of graphene, such as bulk graphene aerogels for a variety of applications. However, these three-dimensional (3D) graphenes exhibit physicochemical property attenuation compared to their 2D building blocks because of one-fold composition and tortuous, stochastic porous networks. These limitations can be offset by developing a graphene composite material with an engineered porous architecture. Here, we report the fabrication of 3D periodic graphene composite aerogel microlattices for supercapacitor applications, via a 3D printing technique known as direct-ink writing. The key factor in developing these novel aerogels is creating an extrudable graphene oxide-based composite ink and modifying the 3D printing method to accommodate aerogel processing. The 3D-printed graphene composite aerogel (3D-GCA) electrodes are lightweight, highly conductive, and exhibit excellent electrochemical properties. In particular, the supercapacitors using these 3D-GCA electrodes with thicknesses on the order of millimeters display exceptional capacitive retention (ca. 90% from 0.5 to 10 A·g(-1)) and power densities (>4 kW·kg(-1)) that equal or exceed those of reported devices made with electrodes 10-100 times thinner. This work provides an example of how 3D-printed materials, such as graphene aerogels, can significantly expand the design space for fabricating high-performance and fully integrable energy storage devices optimized for a broad range of applications.

On-demand and location selective particle assembly via electrophoretic deposition for fabricating structures with particle-to-particle precision.

Programmable positioning of 2 µm polystyrene (PS) beads with single particle precision and location selective, "on-demand", particle deposition was demonstrated by utilizing patterned electrodes and electrophoretic deposition (EPD). An electrode with differently sized hole patterns, from 0.5 to 5 µm, was used to illustrate the discriminatory particle deposition events based on the voltage and particle-to-hole size ratio. With decreasing patterned hole size, a larger electric field was required for a particle deposition event to occur in that hole. For the 5 µm hole, particle deposition began to occur at 10 V/cm where as an electric field of 15 V/cm was required for particles to begin depositing in the 2 µm holes. The likelihood of particle depositions continued to increase for smaller sized holes as the electric field increased. Eventually, a monolayer of particles began to form at approximately 20 V/cm. In essence, a voltage threshold was found for each hole pattern of different sizes, allowing fine adjustments in pattern hole size and voltage to control when a particle deposition event took place, even with the patterns on the same electrode. This phenomenon opens a route toward controlled, multimaterial deposition and assembly onto substrates without repatterning of the electrode or complicated surface modification of the particles. An analytical approach using the theories for electrophoresis and dielectrophoresis found the former to be the dominating force for depositing a particle into a patterned hole. Ebeam lithography was used to pattern spherical holes in precise configurations onto electrode surfaces, where each hole accompanied a polystyrene (PS) particle placement and attachment during EPD. The versatility of e-beam lithography was utilized to create arbitrary pattern configurations to fabricate particle assemblies of limitless configurations, enabling fabrication of unique materials assemblies and interfaces.

Synthesis and characterization of a nanocrystalline diamond aerogel.

Aerogel materials have myriad scientific and technological applications due to their large intrinsic surface areas and ultralow densities. However, creating a nanodiamond aerogel matrix has remained an outstanding and intriguing challenge. Here we report the high-pressure, high-temperature synthesis of a diamond aerogel from an amorphous carbon aerogel precursor using a laser-heated diamond anvil cell. Neon is used as a chemically inert, near-hydrostatic pressure medium that prevents collapse of the aerogel under pressure by conformally filling the aerogel's void volume. Electron and X-ray spectromicroscopy confirm the aerogel morphology and composition of the nanodiamond matrix. Time-resolved photoluminescence measurements of recovered material reveal the formation of both nitrogen- and silicon- vacancy point-defects, suggesting a broad range of applications for this nanocrystalline diamond aerogel.

3D printed optimized electrodes for electrochemical flow reactors.

Recent advances in 3D printing have enabled the manufacture of porous electrodes which cannot be machined using traditional methods. With micron-scale precision, the pore structure of an electrode can now be designed for optimal energy efficiency, and a 3D printed electrode is not limited to a single uniform porosity. As these electrodes scale in size, however, the total number of possible pore designs can be intractable; choosing an appropriate pore distribution manually can be a complex task. To address this challenge, we adopt an inverse design approach. Using physics-based models, the electrode structure is optimized to minimize power losses in a flow reactor. The computer-generated structure is then printed and benchmarked against homogeneous porosity electrodes. We show how an optimized electrode decreases the power requirements by 16% compared to the best-case homogeneous porosity. Future work could apply this approach to flow batteries, electrolyzers, and fuel cells to accelerate their design and implementation.

Interpenetrated Structures for Enhancing Ion Diffusion Kinetics in Electrochemical Energy Storage Devices.

The architectural design of electrodes offers new opportunities for next-generation electrochemical energy storage devices (EESDs) by increasing surface area, thickness, and active materials mass loading while maintaining good ion diffusion through optimized electrode tortuosity. However, conventional thick electrodes increase ion diffusion length and cause larger ion concentration gradients, limiting reaction kinetics. We demonstrate a strategy for building interpenetrated structures that shortens ion diffusion length and reduces ion concentration inhomogeneity. This free-standing device structure also avoids short-circuiting without needing a separator. The feature size and number of interpenetrated units can be adjusted during printing to balance surface area and ion diffusion. Starting with a 3D-printed interpenetrated polymer substrate, we metallize it to make it conductive. This substrate has two individually addressable electrodes, allowing selective electrodeposition of energy storage materials. Using a Zn//MnO2 battery as a model system, the interpenetrated device outperforms conventional separate electrode configurations, improving volumetric energy density by 221% and exhibiting a higher capacity retention rate of 49% compared to 35% at temperatures from 20 to 0 °C. Our study introduces a new EESD architecture applicable to Li-ion, Na-ion batteries, supercapacitors, etc.

Three-Dimensional Printed MoS2/Graphene Aerogel Electrodes for Hydrogen Evolution Reactions.

In this work, we demonstrate the use of direct ink writing (DIW) technology to create 3D catalytic electrodes for electrochemical applications. Hybrid MoS2/graphene aerogels are made by mixing commercially available MoS2 and graphene oxide powders into a thixotropic, high concentration, viscous ink. A porous 3D structure of 2D graphene sheets and MoS2 particles was created after post treatment by freeze-drying and reducing graphene oxide through annealing. The composition and morphology of the samples were fully characterized through XPS, BET, and SEM/EDS. The resulting 3D printed MoS2/graphene aerogel electrodes had a remarkable electrochemically active surface area (>1700 cm2) and were able to achieve currents over 100 mA in acidic media. Notably, the catalytic activity of the MoS2/graphene aerogel electrodes was maintained with minimal loss in surface area compared to the non-3D printed electrodes, suggesting that DIW can be a viable method of producing durable electrodes with a high surface area for water splitting. This demonstrates that 3D printing a MoS2/graphene 3D porous network directly using our approach not only improves electrolyte dispersion and facilitates catalyst utilization but also provides multidimensional electron transport channels for improving electronic conductivity.

A Bioinspired Artificial Injury Response System Based on a Robust Polymer Memristor to Mimic a Sense of Pain, Sign of Injury, and Healing.

Flexible electronic skin with features that include sensing, processing, and responding to stimuli have transformed human-robot interactions. However, more advanced capabilities, such as human-like self-protection modalities with a sense of pain, sign of injury, and healing, are more challenging. Herein, a novel, flexible, and robust diffusive memristor based on a copolymer of chlorotrifluoroethylene and vinylidene fluoride (FK-800) as an artificial nociceptor (pain sensor) is reported. Devices composed of Ag/FK-800/Pt have outstanding switching endurance >106  cycles, orders of magnitude higher than any other two-terminal polymer/organic memristors in literature (typically 102 -103 cycles). In situ conductive atomic force microscopy is employed to dynamically switch individual filaments, which demonstrates that conductive filaments correlate with polymer grain boundaries and FK-800 has superior morphological stability under repeated switching cycles. It is hypothesized that the high thermal stability and high elasticity of FK-800 contribute to the stability under local Joule heating associated with electrical switching. To mimic biological nociceptors, four signature nociceptive characteristics are demonstrated: threshold triggering, no adaptation, relaxation, and sensitization. Lastly, by integrating a triboelectric generator (artificial mechanoreceptor), memristor (artificial nociceptor), and light emitting diode (artificial bruise), the first bioinspired injury response system capable of sensing pain, showing signs of injury, and healing, is demonstrated.

Synthesis of graphene aerogel with high electrical conductivity.

We report the synthesis of ultra-low-density three-dimensional macroassemblies of graphene sheets that exhibit high electrical conductivities and large internal surface areas. These materials are prepared as monolithic solids from suspensions of single-layer graphene oxide in which organic sol-gel chemistry is used to cross-link the individual sheets. The resulting gels are supercritically dried and then thermally reduced to yield graphene aerogels with densities approaching 10 mg/cm(3). In contrast to methods that utilize physical cross-links between GO, this approach provides covalent carbon bonding between the graphene sheets. These graphene aerogels exhibit an improvement in bulk electrical conductivity of more than 2 orders of magnitude (∼1 × 10(2) S/m) compared to graphene assemblies with physical cross-links alone (∼5 × 10(-1) S/m). The graphene aerogels also possess large surface areas (584 m(2)/g) and pore volumes (2.96 cm(3)/g), making these materials viable candidates for use in energy storage, catalysis, and sensing applications.

3D-Printed Structure Boosts the Kinetics and Intrinsic Capacitance of Pseudocapacitive Graphene Aerogels.

The performance of pseudocapacitive electrodes at fast charging rates are typically limited by the slow kinetics of Faradaic reactions and sluggish ion diffusion in the bulk structure. This is particularly problematic for thick electrodes and electrodes highly loaded with active materials. Here, a surface-functionalized 3D-printed graphene aerogel (SF-3D GA) is presented that achieves not only a benchmark areal capacitance of 2195 mF cm-2 at a high current density of 100 mA cm-2 but also an ultrahigh intrinsic capacitance of 309.1 µF cm-2 even at a high mass loading of 12.8 mg cm-2 . Importantly, the kinetic analysis reveals that the capacitance of SF-3D GA electrode is primarily (93.3%) contributed from fast kinetic processes. This is because the 3D-printed electrode has an open structure that ensures excellent coverage of functional groups on carbon surface and facilitates the ion accessibility of these surface functional groups even at high current densities and large mass loading/electrode thickness. An asymmetric device assembled with SF-3D GA as anode and 3D-printed GA decorated with MnO2 as cathode achieves a remarkable energy density of 0.65 mWh cm-2 at an ultrahigh power density of 164.5 mW cm-2 , outperforming carbon-based supercapacitors operated at the same power density.

Nanoscale zirconia as a nonmetallic catalyst for graphitization of carbon and growth of single- and multiwall carbon nanotubes.

We report that nanoparticulate zirconia (ZrO(2)) catalyzes both growth of single-wall and multiwall carbon nanotubes (CNTs) by thermal chemical vapor deposition (CVD) and graphitization of solid amorphous carbon. We observe that silica-, silicon nitride-, and alumina-supported zirconia on silicon nucleates single- and multiwall carbon nanotubes upon exposure to hydrocarbons at moderate temperatures (750 degrees C). High-pressure, time-resolved X-ray photoelectron spectroscopy (XPS) of these substrates during carbon nanotube nucleation and growth shows that the zirconia catalyst neither reduces to a metal nor forms a carbide. Point-localized energy-dispersive X-ray spectroscopy (EDAX) using scanning transmission electron microscopy (STEM) confirms catalyst nanoparticles attached to CNTs are zirconia. We also observe that carbon aerogels prepared through pyrolysis of a Zr(IV)-containing resorcinol-formaldehyde polymer aerogel precursor at 800 degrees C contain fullerenic cage structures absent in undoped carbon aerogels. Zirconia nanoparticles embedded in these carbon aerogels are further observed to act as nucleation sites for multiwall carbon nanotube growth upon exposure to hydrocarbons at CVD growth temperatures. Our study unambiguously demonstrates that a nonmetallic catalyst can catalyze CNT growth by thermal CVD while remaining in an oxidized state and provides new insight into the interactions between nanoparticulate metal oxides and carbon at elevated temperatures.

Colloidal Materials for 3D Printing.

In recent years, 3D printing has led to a disruptive manufacturing revolution that allows complex architected materials and structures to be created by directly joining sequential layers into designed 3D components. However, customized feedstocks for specific 3D printing techniques and applications are limited or nonexistent, which greatly impedes the production of desired structural or functional materials. Colloids, with their stable biphasic nature, have tremendous potential to satisfy the requirements of various 3D printing methods owing to their tunable electrical, optical, mechanical, and rheological properties. This enables materials delivery and assembly across the multiple length scales required for multifunctionality. Here, a state-of-the-art review on advanced colloidal processing strategies for 3D printing of organic, ceramic, metallic, and carbonaceous materials is provided. It is believed that the concomitant innovations in colloid design and 3D printing will provide numerous possibilities for the fabrication of new constructs unobtainable using traditional methods, which will significantly broaden their applications.

Toward digitally controlled catalyst architectures: Hierarchical nanoporous gold via 3D printing.

Monolithic nanoporous metals, derived from dealloying, have a unique bicontinuous solid/void structure that provides both large surface area and high electrical conductivity, making them ideal candidates for various energy applications. However, many of these applications would greatly benefit from the integration of an engineered hierarchical macroporous network structure that increases and directs mass transport. We report on 3D (three-dimensional)-printed hierarchical nanoporous gold (3DP-hnp-Au) with engineered nonrandom macroarchitectures by combining 3D printing and dealloying. The material exhibits three distinct structural length scales ranging from the digitally controlled macroporous network structure (10 to 1000 µm) to the nanoscale pore/ligament morphology (30 to 500 nm) controlled by dealloying. Supercapacitance, pressure drop, and catalysis measurements reveal that the 3D hierarchical nature of our printed nanoporous metals markedly improves mass transport and reaction rates for both liquids and gases. Our approach can be applied to a variety of alloy systems and has the potential to revolutionize the design of (electro-)chemical plants by changing the scaling relations between volume and catalyst surface area.

Negative Additive Manufacturing of Complex Shaped Boron Carbides.

Boron carbide (B4C) is one of the hardest materials in existence. However, this attractive property also limits its machineability into complex shapes for high wear, high hardness, and lightweight material applications such as armors. To overcome this challenge, negative additive manufacturing (AM) is employed to produce complex geometries of boron carbides at various length scales. Negative AM first involves gelcasting a suspension into a 3D-printed plastic mold. The mold is then dissolved away, leaving behind a green body as a negative copy. Resorcinol-formaldehyde (RF) is used as a novel gelling agent because unlike traditional hydrogels, there is little to no shrinkage, which allows for extremely complex molds to be used. Furthermore, this gelling agent can be pyrolyzed to leave behind ~50 wt% carbon, which is a highly effective sintering aid for B4C. Due to this highly homogenous distribution of in situ carbon within the B4C matrix, less than 2% porosity can be achieved after sintering. This protocol highlights in detail the methodology for creating near fully dense boron carbide parts with highly complex geometries.

3D-Printing of Meso-structurally Ordered Carbon Fiber/Polymer Composites with Unprecedented Orthotropic Physical Properties.

Here we report the first example of a class of additively manufactured carbon fiber reinforced composite (AMCFRC) materials which have been achieved through the use of a latent thermal cured aromatic thermoset resin system, through an adaptation of direct ink writing (DIW) 3D-printing technology. We have developed a means of printing high performance thermoset carbon fiber composites, which allow the fiber component of a resin and carbon fiber fluid to be aligned in three dimensions via controlled micro-extrusion and subsequently cured into complex geometries. Characterization of our composite systems clearly show that we achieved a high order of fiber alignment within the composite microstructure, which in turn allows these materials to outperform equivalently filled randomly oriented carbon fiber and polymer composites. Furthermore, our AM carbon fiber composite systems exhibit highly orthotropic mechanical and electrical responses as a direct result of the alignment of carbon fiber bundles in the microscale which we predict will ultimately lead to the design of truly tailorable carbon fiber/polymer hybrid materials having locally programmable complex electrical, thermal and mechanical response.