Flexible, Self-Supported Anode for Organic Batteries with a Matched Hierarchical Current Collector System for Boosted Current Density.

The inherent flexibility of redox-active organic polymers and carbon-based fillers, combined with flexible current collectors (CCs) is ideal for the fabrication of flexible batteries. Herein, a one-step electrophoretic deposition of polyviologen (PV)/graphene-oxide (GO) aqueous composites onto a flexible mesh of 60 µm thick wires, 100 µm apart, is described. Notably, during electrodeposition, GO is transformed into conductive reduced GO (rGO), and nanoscopic pores are formed by self-assembly allowing charge/discharge of the redox sites over dozens of micrometers. Typically, electrodeposition of PV alone on a flat CC (FCC) is limited by its electrically insulating structure to ≈0.15 mAh cm-2 , but the presence of rGO allows thicker active layers without loss in (dis-)charging kinetics and reaching areal capacities of ≈2 mAh cm-2 . Remarkably, when the FCC is replaced by a mesh, the deposition of significantly more anode materials (≈5 mAh cm-2 ) is possible, while the (dis-)charging kinetics is considerably improved. It exhibits high capacity retention at an ultrafast rate of 100 C (<3%) and excellent bending stabilities. This represents the first combination of a microscopic-CC (mesh wires) with a molecular-electronic and -ionic conductor (rGO with its pores), i.e., a hierarchical-CC system with maximized polymer thickness and minimized wire thickness. The stacking of such modified grids paves the road to further increase the areal capacity.

A Maze in Plastic Wastes: Autonomous Motile Photocatalytic Microrobots against Microplastics.

An extremely high quantity of small pieces of synthetic polymers, namely, microplastics, has been recently identified in some of the most intact natural environments, e.g., on top of the Alps and Antarctic ice. This is a "scary wake-up call", considering the potential risks of microplastics for humans and marine systems. Sunlight-driven photocatalysis is the most energy-efficient currently known strategy for plastic degradation; however, attaining efficient photocatalyst-plastic interaction and thus an effective charge transfer in the micro/nanoscale is very difficult; that adds up to the common challenges of heterogeneous photocatalysis including low solubility, precipitation, and aggregation of the photocatalysts. Here, an active photocatalytic degradation procedure based on intelligent visible-light-driven microrobots with the capability of capturing and degrading microplastics "on-the-fly" in a complex multichannel maze is introduced. The robots with hybrid powers carry built-in photocatalytic (BiVO4) and magnetic (Fe3O4) materials allowing a self-propelled motion under sunlight with the possibility of precise actuation under a magnetic field inside the macrochannels. The photocatalytic robots are able to efficiently degrade different synthetic microplastics, particularly polylactic acid, polycaprolactone, thanks to the generated local self-stirring effect in the nanoscale and enhanced interaction with microplastics without using any exterior mechanical stirrers, typically used in conventional systems. Overall, this proof-of-concept study using microrobots with hybrid wireless powers has shown for the first time the possibility of efficient degradation of ultrasmall plastic particles in confined complex spaces, which can impact research on microplastic treatments, with the final goal of diminishing microplastics as an emergent threat for humans and marine ecosystems.

The Metallocene Battery: Ultrafast Electron Transfer Self Exchange Rate Accompanied by a Harmonic Height Breathing.

The first all-metallocene rechargeable battery consisting of poly-cobaltocenium/- and poly-ferrocene/reduced graphene oxide composites as anode and cathode was prepared. The intrinsically fast ET self-exchange rate of metallocenes was successfully combined with an efficient ion-percolation achieved by molecular self-assembly. The resulting battery materials show ideal Nernstian behavior, is thickness scalable up to >1.2 C cm-2 , and exhibit high coulombic efficiency at ultrafast rates (200 A g-1 ). Using aqueous LiClO4 , the charge is carried exclusively by the anion. The ClO4 - intercalation is accompanied by a reciprocal height change of the active layers. Principally, volume changes in organic battery materials during charging/discharging are not desirable and represent a major safety issue. However, here, the individual height changes-due to ion breathing-are reciprocal and thus prohibiting any internal pressure build-up in the closed-cell, leading to excellent cycling stability.

Near-Atomic-Thick Bismuthene Oxide Microsheets for Flexible Aqueous Anodes: Boosted Performance upon 3D → 2D Transition.

Aqueous batteries provide safety, but they usually suffer from low energy and short lifetimes, limiting their use for large-scale energy storage. Two-dimensional materials with infinite lateral dimensions have inherent properties such as high surface area and remarkable power density and cycling stability that are shown to be critical for the next generation of energy storage systems. Here, ultrathin bismuthene oxide with a large aspect ratio is studied as an anode material for rechargeable aqueous metal-ion batteries. The metal oxides are prepared via a novel electrochemical system allowing for a smooth, high-quality transition of bismuthene to bismuthene oxide in a short time. This anodic system is shown to overcome major limiting factors of such batteries, including low capacity and irreversible and unstable redox reactions in aqueous electrolytes. The essential energy storage properties of two-dimensional (2D) microsheets, without the addition of conductive additives and binders, are compared with those of the corresponding three-dimensional (3D) structures. Notably, the battery performance of 2D microsheets is significantly better than that of nanoparticles from all examined aspects, including power density and potential and cycling stability, while exhibiting a capacity density close to their theoretical value. Moreover, 2D microsheets have shown impressive mechanical flexibility related to the ultrathin thickness of individual microsheets and strong interaction between them after film deposition. Combining the excellent energy storage properties of bismuthene oxide, the simple electrode preparation procedure, the inherent flexing characteristic, and the nontoxicity of both the battery material and the electrolyte makes this 2D material an exceptional candidate for large-scale wearable green electronics.

Bismuthene Metallurgy: Transformation of Bismuth Particles to Ultrahigh-Aspect-Ratio 2D Microsheets.

Ultrathin bismuth exhibits promising performance for topological insulators due to its narrow band gap and intrinsic strong spin-orbit coupling, as well as for energy-related applications because of its electronic and mechanical properties. However, large-scale production of 2D sheets via liquid-phase exfoliation as an established large-scale method is restricted by the strong interaction between bismuth layers. Here, a sonication method is utilized to produce ultrahigh-aspect-ratio bismuthene microsheets. The studies on the mechanism excludes the exfoliation of the layered bulk bismuth and formation of the microsheets is attributed to the melting of spherical particles (r = 1.5 µm) at a high temperature-generated under the ultrasonic tip-followed by a recrystallization step producing uniformly-shaped ultrathin microsheets (A = 0.5-2 µm2 , t: ≈2 nm). Notably, although the preparation is performed in oxygenated aqueous solution, the sheets are not oxidized, and they are stable under ambient conditions for at least 1 month. The microsheets are used to construct a vapor sensor using electrochemical impedance spectroscopy as detection technique. The device is highly selective, and it shows long-term stability. Overall, this project exhibits a reproducible method for large-scale preparation of ultrathin bismuthene microsheets in a benign environment, demonstrating opportunities to realize devices based on bismuthene.

Active Anion Delivery by Self-Propelled Microswimmers.

Self-propelled micro- and nanomachines are at the forefront of materials research, branching into applications in biomedical science and environmental remediation. Cationic frameworks enabling the collection and delivery of anionic species (A-) are highly required, due to the large variety of life-threatening pollutants, such as radioactive technetium and carcinogenic chromium, and medicines, such as dexamethasone derivatives with negative charges. However, such autonomous moving carriers for active transport of the anions have been barely discussed. A polymeric viologen (PV++)-consisting of electroactive bicationic subunits-is utilized in a tubular autonomous microswimmer to selectively deliver A- of different sizes and charge densities. The cargo loading is based on a facile anion exchange mechanism. The packed crystal structure of PV++ allows removal of an exceptionally high quantity of anions per one microswimmer (2.55 × 10-13 mol anions per microswimmer), a critical factor often neglected regarding the real-world application of microswimmers. Notably, there was virtually no leakage of anions during the delivery process or upon keeping the loaded microswimmers under ambient conditions for at least 4 months. Multiple release mechanisms, compatible with different environments, including electrochemical, photochemical, and a metathesis reaction, with high efficiencies up to 98% are introduced. Such functional autonomous micromachines provide great promise for the next generation of functional materials for biomedical and environmental applications.

Functional 2D Germanene Fluorescent Coating of Microrobots for Micromachines Multiplexing.

Micromachines are at the forefront of materials research as they are self-propelled, smart autonomous systems capable of acting as an intelligent matter. One of the obstacles the field faces is tracking individual micromachines carrying molecular cargo from the rest of the micromachines. Highly stable fluorescent markers based on chemically modified 2D germanene compounds are developed. Two different 2D germanene derivatives, 4-fluorophenylgermanane (2D-Ph-Ge) and methylgermanane (2D-Me-Ge), exhibit different fluorescence under UV light irradiation (excitation at 365 nm), which allows one particular micromotor to be easily distinguished in a mixture of micromotors. This offers a paradigm shift toward a new approach of multiplex detection of self-propelled micromachines. The utility is demonstrated on a drug delivery system, where micromachines carrying a drug are labeled with 2D-Ph-Ge with blue emission while bare micromachines are labeled by 2D-Me-Ge with red emission. This approach of functional fluorescent labeling will pave the way to multiple simultaneous functionalized micromachines identification in complex environments.

Supercapacitors in Motion: Autonomous Microswimmers for Natural-Resource Recovery.

An electroadsorption technique similar to the ultrafast charging mechanism in supercapacitors is utilized to remove metals with different sizes and hydrophilicities from contaminated water using self-propelled microswimmers. The swimmers carry graphite fibre or bismuth with a layered crystal structure providing high electrostatic double-layer capacitances. Unlike previous methods, this electrochemical technique does not only utilize the surface of the swimmers, but due to the interlayer spacing of the graphite and bismuth, it is able to store metals in ≈400 layers, allowing removal and recovery of >50 ppm lithium in only 5 min. A larger interlayer distance between bismuth sheets allows the removal of bigger cations (sodium and calcium), expanding the application of this method to a large variety of natural elements. Finally, magnetic navigation of charged swimmers to an oxygen-saturated media causes oxidation and thus immediate release of the metal ions from the swimmers.

In Situ Doping of Black Phosphorus by High-Pressure Synthesis.

Black phosphorus is a two-dimensional semiconductor with promising properties for catalysis, energy storage, and conversion as well as electronic device applications, and control of its electronic structure is critical for such applications. Substitutional doping of phosphorus by electron donating (e.g., sulfur) or electron accepting elements (e.g., germanium) can significantly change its properties, especially charge carrier concentration. Here, we report the in situ doping of black phosphorus by its direct synthesis from a mixture of red phosphorus and a dopant by high pressure synthesis. In detail, we study the incorporation of germanium, sulfur, selenium, and tellurium within black phosphorus, showing significant differences in incorporation of individual elements and assess their suitability for potential electrochemical applications.

Recyclable nanographene-based micromachines for the on-the-fly capture of nitroaromatic explosives.

It has been more than a decade since nano/micromachines (NMMs) have received the particular attention of scientists in different research fields. They are able to convert chemical energy into mechanical motion in their surrounding environment. Herein, a powerful, efficient and fast strategy of using nanosized reduced graphene oxide flake (n-rGO)-based self-propelled tubular micromachines for the removal of nitroaromatic compounds (NACs) is described. This method relies on the integration of the rGO as a well-known adsorbent of aromatic compounds with chemically powered engines for the removal of explosive compounds such as 2,4,6-trinitrotoluene (TNT), 2,4,6-trinitrophenol (TNP) and 2,4-dinitrotoluene (DNT). Nanographene oxide reduced electrochemically inside the pores of the polycarbonate membrane to form an outer layer (n-rGO, adsorbent layer) of the micromachines. Subsequent electrodeposition of nickel (Ni, magnetic layer) and platinum (Pt, catalytic layer) resulted in the formation of n-rGO/Ni/Pt micromachines. Notably, the bubble-propelled micromachines were able to remove nitroaromatic compounds with high efficiency (∼90-92%) compared to the efficiency of magnetic-guided (22-42%) and static (2.5-7%) micromachines. Most importantly, the micromachines were regenerated and reused several times. The regeneration is based on an electrochemical method in which electron injection into the machine causes the expulsion of contaminants from the outer layer of the micromachines within a few seconds. The integration of the powerful self-propulsion, high adsorbent capacity of rGO and the introduced ultrafast regeneration procedure are beneficial for the realization of an active platform for water remediation.

Recoverable Bismuth-Based Microrobots: Capture, Transport, and On-Demand Release of Heavy Metals and an Anticancer Drug in Confined Spaces.

Self-propelled microrobots are seen as the next step of micro- and nanotechnology. The biomedical and environmental applications of these robots in the real world need their motion in the confined environments, such as in veins or spaces between the grains of soil. Here, self-propelled trilayer microrobots have been prepared using electrodeposition techniques, coupling unique properties of green bismuth (Bi) with a layered crystal structure, magnetic nickel (Ni), and a catalytic platinum (Pt) layer. These Bi-based microrobots are investigated as active self-propelled platforms that can load, transfer, and release both doxorubicin (DOX), as a widely used anticancer drug, and arsenic (As) and chromium (Cr), as hazardous heavy metals. The significantly high loading capability for such variable cargoes is due to the high surface area provided by the rhombohedral layered crystal structure of bismuth, as well as the defects introduced through the oxide layer formed on the surface of bismuth. The drug release is based on an ultrafast electroreductive mechanism in which the electron injection into microrobots and consequently into the loaded objects causes an electrostatic repulsion between them and thus an ultrafast release of the loaded cargos. Remarkably, we have presented magnetic control of the Bi-based microrobots inside a microfluidic system equipped with an electrochemical setup as a proof-of-concept to demonstrate (i) heavy metals/DOX loading, (ii) a targeted transport system, (iii) the on-demand release mechanism, and (iv) the recovery of the robots for further usage.

2D-Pnictogens: alloy-based anode battery materials with ultrahigh cycling stability.

There is an increasing demand for efficient energy storage systems in our modern mobile society for a wide range of applications such as smart grids, portable electronic devices, and electric vehicles. The performance of advanced batteries in terms of energy density, power density, cyclability, and safety is mainly determined by the primary functional components, particularly by the electrode materials. Black phosphorus (BP) and the following elements in group V (pnictogens) including arsenic, antimony, and bismuth with layered structures have attracted tremendous attention to replace the graphite anode. This is due to their extremely high specific-capacities for lithium and sodium storage based on the alloying reaction mechanism; however, the same mechanism causes an irreversible volume expansion and thus low cycling stability. Since the discovery of single layer BP and its outstanding physical properties such as tunable band gap, strong in-plane anisotropy, and high carrier mobility, the battery community have intensively studied this material as well as the 2D structures of other pnictogens. In this review, first, the preparation and properties of 2D-pnictogens including crystal structure and chemical stability are briefly described. Second, the theoretical and experimental details of the intercalation and alloying mechanisms are discussed. Finally, the excellent performance of 2D-pnictogens for lithium ion and sodium ion batteries and their principal advantages compared to their parent 3D structures are presented.

High Performance Poly(viologen)-Graphene Nanocomposite Battery Materials with Puff Paste Architecture.

Four linear poly(viologens) (PV1, PV2: phenylic, PV3: benzylic, and PV4: aliphatic) in tight molecular contact with reduced graphene oxide (rGO), that is, PV@rGO, were prepared and used as anodic battery materials. These composites show exceptionally high, areal, volumetric, and current densities, for example, PV1@rGO composites (with 15 wt % rGO, corresponding to 137 mAh g-1) show 13.3 mAh cm-2 at 460 µm and 288 mAh cm-3 with 98% Coulombic efficiency at current densities up to 1000 A g-1, better than any reported organic materials. These remarkable performances are based on (i) molecular self-assembling of PVs on individual GO sheets yielding colloidal PV@GO and (ii) efficient GO/rGO transformation electrocatalyzed by PVs. Ion breathing during charging/discharging was studied by electrochemical quartz crystal microbalance and electrochemical atomic force microscopy revealing an absolute reversible and strongly anisotropic thickness oscillation of PV1@rGO at a right angle to the macroscopic current collector. It is proposed that such stress-free breathing is the key property for good cyclability of the battery material. The anisotropy is related to a puff paste architecture of rGO sheets parallel to the macroscopic current collector. A thin graphite sheet electrode with an areal capacity of 1.23 mAh cm-2 is stable over 200 bending cycles, making the material applicable for wearable electronics. The polymer acts as a lubricant between the rGO layers if shearing forces are active.