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.

NiF2 Nanorod Arrays for Supercapattery Applications.

A electrode for energy storage cells is possible directly on Ni foam, using a simple reduction process to form NiF2 nanorod arrays (NA). We demonstrate NiF2@Ni NA for a symmetric electrochemical supercapattery electrode. With an areal specific capacitance of 51 F cm-2 at 0.25 mA cm-2 current density and 94% cycling stability, a NiF2@Ni electrode can exhibit supercapattery behavior, a combination of supercapacitor and battery-like redox. The symmetric electrochemical supercapattery delivers 31 W h m-2 energy density and 797 W m-2 power density with 83% retention in a 1 M KOH electrolyte, constituting a step toward manufacturing a laboratory-scale energy storage device based on metal halides. Producing self-grown hierarchically porous nanostructured electrodes on three-dimensional metal foams by displacement reactions may be useful for other metal halides as electrodes for supercapacitors, supercapatteries, and lithium-ion batteries.

Germanium tin alloy nanowires as anode materials for high performance Li-ion batteries.

The combination of two active Li-ion materials (Ge and Sn) can result in improved conduction paths and higher capacity retention. Here we report for the first time, the implementation of Ge1-x Sn x alloy nanowires as anode materials for Li-ion batteries. Ge1-x Sn x alloy nanowires have been successfully grown via vapor-liquid-solid technique directly on stainless steel current collectors. Ge1-x Sn x (x = 0.048) nanowires were predominantly seeded from the Au0.80Ag0.20 catalysts with negligible amount of growth was also directly catalyzed from stainless steel substrate. The electrochemical performance of the the Ge1-x Sn x nanowires as an anode material for Li-ion batteries was investigated via galvanostatic cycling and detailed analysis of differential capacity plots (DCPs). The nanowire electrodes demonstrated an exceptional capacity retention of 93.4% from the 2nd to the 100th charge at a C/5 rate, while maintaining a specific capacity value of ∼921 mAh g-1 after 100 cycles. Voltage profiles and DCPs revealed that the Ge1-x Sn x nanowires behave as an alloying mode anode material, as reduction/oxidation peaks for both Ge and Sn were observed, however it is clear that the reversible lithiation of Ge is responsible for the majority of the charge stored.

Author Correction: Low-Temperature Ionic Layer Adsorption and Reaction Grown Anatase TiO2 Nanocrystalline Films for Efficient Perovskite Solar Cell and Gas Sensor Applications.

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Evaluating the Surface Chemistry of Black Phosphorus during Ambient Degradation.

Black phosphorus (BP) is emerging as a promising candidate for electronic, optical, and energy storage applications. However, its poor ambient stability remains a critical challenge. Evaluation of few-layer liquid-exfoliated BP during ambient exposure using X-ray photoelectron spectroscopy and attenuated total reflectance Fourier transform infrared spectroscopy allows its surface chemistry to be investigated. Oxidation of liquid-exfoliated few-layer BP initially occurs through nonbridging oxide species, which convert to bridging oxide species after ambient exposure. We demonstrate the instability of these bridging oxide species, which undergo hydrolysis to form volatile phosphorus oxides and evaporate from the BP surface. FTIR spectroscopy, scanning transmission electron microscopy, and atomic force microscopy were used to confirm the formation of liquid oxides through a continuous oxidation cycle that results in the decomposition of BP. Furthermore, we show that the instability of few-layer BP originates from the formation of bridging oxide species.

Standardization of research methods employed in assessing the interaction between metallic-based nanoparticles and the blood-brain barrier: Present and future perspectives.

Treating diseases of the central nervous system (CNS) is complicated by the presence of the blood-brain barrier (BBB), a semipermeable boundary layer protecting the CNS from toxins and homeostatic disruptions. However, this layer also excludes almost 100% of therapeutics, impeding the treatment of CNS diseases. The advent of nanoparticles, in particular metallic-based nanoparticles, presents the potential to overcome this barrier and transport drugs into the CNS. Recent interest in metallic-based nanoparticles has generated an immense array of information pertaining to nanoparticles of different materials, sizes, morphologies, and surface properties. Nanoparticles with different physico-chemical properties lead to distinct nanoparticle-host interactions; yet, comprehensive characterization is often not completed. Similarly, in vivo testing has involved a mixed evaluation of parameters, including: BBB permeability, integrity, biodistribution, and toxicity. The methods applied to assess these parameters are inconsistent; this complicates the comparison of different nanoparticle-host system responses. A systematic review was conducted to investigate the methods by which metallic-based nanoparticles are characterized and assessed in vivo. The introduction of a standardized approach to nanoparticle characterization and in vivo testing is crucial if research is to transition to a clinical setting. The approach suggested, herein, is based on equipment and techniques that are accessible and informative to facilitate the routine incorporation of this standardized, informative approach into different research settings. Thorough characterization could lead to improved interpretation of in vivo responses, which could clarify nanoparticle properties that result in favorable in vivo outcomes whilst exposing nanoparticle-specific weaknesses. Only then will researchers successfully identify nanoparticles capable of delivering life-saving therapeutics across the blood-brain barrier.

Hybrid composite polyaniline-nickel hydroxide electrode materials for supercapacitor applications.

Pristine and nanocomposite (NC) hybrid electrodes of polyaniline (PANI)-nickel hydroxide [Ni(OH)2] have been prepared by single and two-step electrodeposition processes, respectively, onto stainless-steel (SS) substrates. Enhanced reversibility and stability of amorphous PANI- Ni(OH)2 NC electrodes compared to single electrode materials have been explored. PANI has a nanofibrous morphology, Ni(OH)2 has nanoplatelet-type morphology, and the NC electrodes retain an overall nanofibrous morphology. The maximum specific capacitance (SC), obtained from integrated charge under voltammetric conditions, for PANI (electro-deposited for 5 min), NC (electrodeposition of Ni(OH)2 for 10 min and 20 min onto PANI electrode surface) and Ni(OH)2 (electrodeposited for 10 min) electrodes, are 0.59, 39.06, 32.36, and 113.8 F/g, respectively, suggesting higher electrochemical performance of Ni(OH)2 electrode compared to PANI and NC electrodes. The retention in SC values with faster scan rates from 10 to 100 mV/s for PANI, NC (10 min), NC (20 min) and Ni(OH)2 are 38.7, 61.1, 52.4, and 29.0 %, respectively, explicitly confirming a higher reversibility in NC electrodes. The retention in SC values with increase of cycle number up to 1000 for PANI, NC (10 min), NC (20 min) and Ni(OH)2 electrodes are 34.9, 61.5, 67.5, and 40.7 % respectively, demonstrating higher electrochemical stability of NC electrodes over pure-phase electrodes. Nearly 2.15, 79.36, 66.66 and 406.83 mC/cm2 charges on PANI, NC (10 min), NC (20 min) and Ni(OH)2 electrodes, respectively, are obtained. Inner to total charge and outer to total charge ratios have been used to explain contributing sites to total charge in pristine and NC electrodes.

Low-Temperature Ionic Layer Adsorption and Reaction Grown Anatase TiO2 Nanocrystalline Films for Efficient Perovskite Solar Cell and Gas Sensor Applications.

A low-temperature (90 °C) and directly grown anatase titanium dioxide (TiO2) nanocrystalline film using successive ionic layer adsorption and reaction (SILAR) for perovskite solar cell and gas sensor applications. TiO2 nanocrystalline electron transfer layer (ETL) improves the power conversion efficiency (PCE) of perovskite solar cells due to faster charge transport kinetics as well as slower charge recombination process. The optimized TiO2 nanocrystalline ETL (15 L) demonstrates as high as ~10% PCE with a short circuit current density of 18.0 mA/cm2, open circuit voltage of 0.81 V and fill factor of 66.3% in perovskite solar cells. Furthermore, room-temperature ammonia sensing characteristics of TiO2 nanocrystalline film (25 L) were  demonstrated for various concentration levels of ammonia in dry air conditions. A high room-temperature response of 80% was achieved at 100 ppm of ammonia with rapid response and recovery signatures of 30 and 85 s, and nearly fifteen days stability, respectively. The response of the sensor to other gases such as formaldehyde, petrol, ethanol acetone, and ammonia etc, indicated a high selectivity towards volatile organic compounds of ammonia gas. The room temperature operation, with high selectivity, repeatability and fast transition times, suggests potentially useful in flexible and cost-effective production in optoelectrochemical device technology.

Polysulfide Binding to Several Nanoscale Magnéli Phases Synthesized in Carbon for Long-Life Lithium-Sulfur Battery Cathodes.

In Li-S batteries, it is important to ensure efficient reversible conversion of sulfur to lithium polysulfide (LiPS). Shuttling effects caused by LiPS dissolution can lead to reduced performance and cycle life. Although carbon materials rely on physical trapping of polysulfides, polar oxide surfaces can chemically bind LiPS to improve the stability of sulfur cathodes. We show a simple synthetic method that allows high sulfur loading into mesoporous carbon preloaded with spatially localized nanoparticles of several Magnéli-phase titanium oxide (Tin O2n-1 ). This material simultaneously suppresses polysulfide shuttling phenomena by chemically binding Li polysulfides onto several Magnéli-phase surfaces in a single cathode and ensures physical confinement of sulfur and LiPS. The synergy between chemical immobilization of significant quantities of LiPS at the surface of several Tin O2n-1 phases and physical entrapment results in coulombically efficient high-rate cathodes with long cycle life and high capacity. These cathodes function efficiently at low electrolyte-to-sulfur ratios to provide high gravimetric and volumetric capacities in comparison with their highly porous carbon counterparts. Assembled coin cells have an initial discharge capacity of 1100 mAh g-1 at 0.1C and maintain a reversible capacity of 520 mAh g-1 at 0.2C for more than 500 cycles. Even at 1C, the cell loses only 0.06 % per cycle for 1000 cycles with a coulombic efficiency close to 99 %.

Metal-free heterogeneous and mesoporous biogenic graphene-oxide nanoparticle-catalyzed synthesis of bioactive benzylpyrazolyl coumarin derivatives.

We report the preparation of graphene oxide nanoparticles (GONPs), a metal-free, heterogeneous, non-toxic, reusable and mesoporous green-(acid)-catalyst obtained by sugar carbonization through a micro-wave chemical synthesis method for the synthesis of bio-active benzylpyrazolyl coumarin derivatives (BCDs) under thermal conditions (50 °C) in ethanol solvent. The obtained products were purified by re-crystallization from ethanol, assuring usability of GONPs in multicomponent reactions (MCRs) that could find wide application in the synthesis of a variety of biologically potent molecules of therapeutic significance.

Functionalization of SiO2 Surfaces for Si Monolayer Doping with Minimal Carbon Contamination.

Monolayer doping (MLD) involves the functionalization of semiconductor surfaces followed by an annealing step to diffuse the dopant into the substrate. We report an alternative doping method, oxide-MLD, where ultrathin SiO2 overlayers are functionalized with phosphonic acids for doping Si. Similar peak carrier concentrations were achieved when compared with hydrosilylated surfaces (∼2 × 1020 atoms/cm3). Oxide-MLD offers several advantages over conventional MLD, such as ease of sample processing, superior ambient stability, and minimal carbon contamination. The incorporation of an oxide layer minimizes carbon contamination by facilitating attachment of carbon-free precursors or by impeding carbon diffusion. The oxide-MLD strategy allows selection of many inexpensive precursors and therefore allows application to both p- and n-doping. The phosphonic acid-functionalized SiO2 surfaces were investigated using X-ray photoelectron spectroscopy and attenuated total reflectance Fourier transform infrared spectroscopy, whereas doping was assessed using electrochemical capacitance voltage and Hall measurements.

Natural Carbonized Sugar as a Low-Temperature Ammonia Sensor Material: Experimental, Theoretical, and Computational Studies.

Carbonized sugar (CS) has been synthesized via microwave-assisted carbonization of market-quality tabletop sugar bearing in mind the advantages of this synthesis method, such as being useful, cost-effective, and eco-friendly. The as-prepared CS has been characterized for its morphology, phase purity, type of porosity, pore-size distribution, and so on. The gas-sensing properties of CS for various oxidizing and reducing gases are demonstrated at ambient temperature, where we observe good selectivity toward liquid ammonia among other gases. The highest ammonia response (50%) of a CS-based sensor was noted at 80 °C for 100 ppm concentration. The response and recovery times of the CS sensor are 180 and 216 s, respectively. This unveiling ammonia-sensing study is explored through a plausible theoretical mechanism, which is further well-supported by computational modeling performed using density function theory. The effect of relative humidity on the CS sensor has also been studied at ambient temperature, which demonstrated that the minimum and maximum (20-100%) relative humidity values revealed 16 and 62% response, respectively.

Large Block Copolymer Self-Assembly for Fabrication of Subwavelength Nanostructures for Applications in Optics.

Nanostructured surfaces are common in nature and exhibit properties such as antireflectivity (moth eyes), self-cleaning (lotus leaf), iridescent colors (butterfly wings), and water harvesting (desert beetles). We now understand such properties and can mimic some of these natural structures in the laboratory. However, these synthetic structures are limited since they are not easily mass produced over large areas due to the limited scalability of current technologies such as UV-lithography, the high cost of infrastructure, and the difficulty in nonplanar surfaces. Here, we report a solution process based on block copolymer (BCP) self-assembly to fabricate subwavelength structures on large areas of optical and curved surfaces with feature sizes and spacings designed to efficiently scatter visible light. Si nanopillars (SiNPs) with diameters of ∼115 ± 19 nm, periodicity of 180 ± 18 nm, and aspect ratio of 2-15 show a reduction in reflectivity by a factor of 100, <0.16% between 400 and 900 nm at an angle of incidence of 30°. Significantly, the reflectivity remains below 1.75% up to incident angles of 75°. Modeling the efficiency of a SiNP PV suggests a 24.6% increase in efficiency, representing a 3.52% (absolute) or 16.7% (relative) increase in electrical energy output from the PV system compared to AR-coated device.

Carbon-Coated Honeycomb Ni-Mn-Co-O Inverse Opal: A High Capacity Ternary Transition Metal Oxide Anode for Li-ion Batteries.

We present the formation of a carbon-coated honeycomb ternary Ni-Mn-Co-O inverse opal as a conversion mode anode material for Li-ion battery applications. In order to obtain high capacity via conversion mode reactions, a single phase crystalline honeycombed IO structure of Ni-Mn-Co-O material was first formed. This Ni-Mn-Co-O IO converts via reversible redox reactions and Li2O formation to a 3D structured matrix assembly of nanoparticles of three (MnO, CoO and NiO) oxides, that facilitates efficient reactions with Li. A carbon coating maintains the structure without clogging the open-worked IO pore morphology for electrolyte penetration and mass transport of products during cycling. The highly porous IO was compared in a Li-ion half-cell to nanoparticles of the same material and showed significant improvement in specific capacity and capacity retention. Further optimization of the system was investigated by incorporating a vinylene carbonate additive into the electrolyte solution which boosted performance, offering promising high-rate performance and good capacity retention over extended cycling. The analysis confirms the possibility of creating a ternary transition metal oxide material with binder free accessible open-worked structure to allow three conversion mode oxides to efficiently cycle as an anode material for Li-ion battery applications.

Liquid-Phase Monolayer Doping of InGaAs with Si-, S-, and Sn-Containing Organic Molecular Layers.

The functionalization and subsequent monolayer doping of InGaAs substrates using a tin-containing molecule and a compound containing both silicon and sulfur was investigated. Epitaxial InGaAs layers were grown on semi-insulating InP wafers and functionalized with both sulfur and silicon using mercaptopropyltriethoxysilane and with tin using allyltributylstannane. The functionalized surfaces were characterized using X-ray photoelectron spectroscopy (XPS). The surfaces were capped and subjected to rapid thermal annealing to cause in-diffusion of dopant atoms. Dopant diffusion was monitored using secondary ion mass spectrometry. Raman scattering was utilized to nondestructively determine the presence of dopant atoms, prior to destructive analysis, by comparison to a blank undoped sample. Additionally, due to the As-dominant surface chemistry, the resistance of the functionalized surfaces to oxidation in ambient conditions over periods of 24 h and 1 week was elucidated using XPS by monitoring the As 3d core level for the presence of oxide components.

Influence of Binders and Solvents on Stability of Ru/RuOx Nanoparticles on ITO Nanocrystals as Li-O2 Battery Cathodes.

Fundamental research on Li-O2 batteries remains critical, and the nature of the reactions and stability are paramount for realising the promise of the Li-O2 system. We report that indium tin oxide (ITO) nanocrystals with supported 1-2 nm oxygen evolution reaction (OER) catalyst Ru/RuOx nanoparticles (NPs) demonstrate efficient OER processes, reduce the recharge overpotential of the cell significantly and maintain catalytic activity to promote a consistent cycling discharge potential in Li-O2 cells even when the ITO support nanocrystals deteriorate from the very first cycle. The Ru/RuOx nanoparticles lower the charge overpotential compared with those for ITO and carbon-only cathodes and have the greatest effect in DMSO electrolytes with a solution-processable F-free carboxymethyl cellulose (CMC) binder (<3.5 V) instead of polyvinylidene fluoride (PVDF). The Ru/RuOx /ITO nanocrystalline materials in DMSO provide efficient Li2 O2 decomposition from within the cathode during cycling. We demonstrate that the ITO is actually unstable from the first cycle and is modified by chemical etching, but the Ru/RuOx NPs remain effective OER catalysts for Li2 O2 during cycling. The CMC binders avoid PVDF-based side-reactions and improve the cyclability. The deterioration of the ITO nanocrystals is mitigated significantly in cathodes with a CMC binder, and the cells show good cycle life. In mixed DMSO-EMITFSI [EMITFSI=1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide] ionic liquid electrolytes, the Ru/RuOx /ITO materials in Li-O2 cells cycle very well and maintain a consistently very low charge overpotential of 0.5-0.8 V.

2D and 3D photonic crystal materials for photocatalysis and electrochemical energy storage and conversion.

This perspective reviews recent advances in inverse opal structures, how they have been developed, studied and applied as catalysts, catalyst support materials, as electrode materials for batteries, water splitting applications, solar-to-fuel conversion and electrochromics, and finally as photonic photocatalysts and photoelectrocatalysts. Throughout, we detail some of the salient optical characteristics that underpin recent results and form the basis for light-matter interactions that span electrochemical energy conversion systems as well as photocatalytic systems. Strategies for using 2D as well as 3D structures, ordered macroporous materials such as inverse opals are summarized and recent work on plasmonic-photonic coupling in metal nanoparticle-infiltrated wide band gap inverse opals for enhanced photoelectrochemistry are provided.

Supercapattery Based on Binder-Free Co3(PO4)2·8H2O Multilayer Nano/Microflakes on Nickel Foam.

A binder-free cobalt phosphate hydrate (Co3(PO4)2·8H2O) multilayer nano/microflake structure is synthesized on nickel foam (NF) via a facile hydrothermal process. Four different concentrations (2.5, 5, 10, and 20 mM) of Co2+ and PO4-3 were used to obtain different mass loading of cobalt phosphate on the nickel foam. The Co3(PO4)2·8H2O modified NF electrode (2.5 mM) shows a maximum specific capacity of 868.3 C g-1 (capacitance of 1578.7 F g-1) at a current density of 5 mA cm-2 and remains as high as 566.3 C g-1 (1029.5 F g-1) at 50 mA cm-2 in 1 M NaOH. A supercapattery assembled using Co3(PO4)2·8H2O/NF as the positive electrode and activated carbon/NF as the negative electrode delivers a gravimetric capacitance of 111.2 F g-1 (volumetric capacitance of 4.44 F cm-3). Furthermore, the device offers a high specific energy of 29.29 Wh kg-1 (energy density of 1.17 mWh cm-3) and a specific power of 4687 W kg-1 (power density of 187.5 mW cm-3).

The structural conversion from α-AgVO3 to ß-AgVO3: Ag nanoparticle decorated nanowires with application as cathode materials for Li-ion batteries.

The majority of electrode materials in batteries and related electrochemical energy storage devices are fashioned into slurries via the addition of a conductive additive and a binder. However, aggregation of smaller diameter nanoparticles in current generation electrode compositions can result in non-homogeneous active materials. Inconsistent slurry formulation may lead to inconsistent electrical conductivity throughout the material, local variations in electrochemical response, and the overall cell performance. Here we demonstrate the hydrothermal preparation of Ag nanoparticle (NP) decorated α-AgVO3 nanowires (NWs) and their conversion to tunnel structured ß-AgVO3 NWs by annealing to form a uniform blend of intercalation materials that are well connected electrically. The synthesis of nanostructures with chemically bound conductive nanoparticles is an elegant means to overcome the intrinsic issues associated with electrode slurry production, as wire-to-wire conductive pathways are formed within the overall electrode active mass of NWs. The conversion from α-AgVO3 to ß-AgVO3 is explained in detail through a comprehensive structural characterization. Meticulous EELS analysis of ß-AgVO3 NWs offers insight into the true ß-AgVO3 structure and how the annealing process facilitates a higher surface coverage of Ag NPs directly from ionic Ag content within the α-AgVO3 NWs. Variations in vanadium oxidation state across the surface of the nanowires indicate that the ß-AgVO3 NWs have a core-shell oxidation state structure, and that the vanadium oxidation state under the Ag NP confirms a chemically bound NP from reduction of diffused ionic silver from the α-AgVO3 NWs core material. Electrochemical comparison of α-AgVO3 and ß-AgVO3 NWs confirms that ß-AgVO3 offers improved electrochemical performance. An ex situ structural characterization of ß-AgVO3 NWs after the first galvanostatic discharge and charge offers new insight into the Li+ reaction mechanism for ß-AgVO3. Ag+ between the van der Waals layers of the vanadium oxide is reduced during discharge and deposited as metallic Ag, the vacant sites are then occupied by Li+.

Growing Oxide Nanowires and Nanowire Networks by Solid State Contact Diffusion into Solution-Processed Thin Films.

New techniques to directly grow metal oxide nanowire networks without the need for initial nanoparticle seed deposition or postsynthesis nanowire casting will bridge the gap between bottom-up formation and top-down processing for many electronic, photonic, energy storage, and conversion technologies. Whether etched top-down, or grown from catalyst nanoparticles bottom-up, nanowire growth relies on heterogeneous material seeds. Converting surface oxide films, ubiquitous in the microelectronics industry, to nanowires and nanowire networks by the incorporation of extra species through interdiffusion can provide an alternative deposition method. It is shown that solution-processed thin films of oxides can be converted and recrystallized into nanowires and networks of nanowires by solid-state interdiffusion of ionic species from a mechanically contacted donor substrate. NaVO3 nanowire networks on smooth Si/SiO2 and granular fluorine-doped tin oxide surfaces can be formed by low-temperature annealing of a Na diffusion species-containing donor glass to a solution-processed V2 O5 thin film, where recrystallization drives nanowire growth according to the crystal habit of the new oxide phase. This technique illustrates a new method for the direct formation of complex metal oxide nanowires on technologically relevant substrates, from smooth semiconductors, to transparent conducting materials and interdigitated device structures.