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Segregated Network Polymer Composites with High Electrical Conductivity and Well Mechanical Properties based on PVC, P(VDFTFE), UHMWPE, and rGO
2020, Shiyanova, Kseniya A., Gudkov, Maksim V., Gorenberg, Arkady Ya, Rabchinskii, Maxim K., Smirnov, Dmitry A., Shapetina, Maria A., Gurinovich, Tatiana D., Goncharuk, Galina P., Kirilenko, Demid A., Bazhenov, Sergey L., Melnikov, Valery P.
The formation of a segregated network structure (wittingly uneven distribution of a filler) is one of the most promising strategies for the fabrication of electrically conductive polymer composites at present. However, the simultaneous achievement of high values of electrical conductivity with the retention of well mechanical properties within this approach remains a great challenge. Here, by means of X-ray photoelectron spectra (XPS), near-edge X-ray absorption fine structure (NEXAFS) spectra, scanning electron microscopy (SEM), dielectric spectroscopy, and compression engineering stress-strain curve analysis, we have studied the effect of a segregated network structure on the electrical conductivity and mechanical properties of a set of polymer composites. The composites were prepared by applying graphene oxide (GO) with ultralarge basal plane size (up to 150 μm) onto the surface of polymer powder particles, namely, poly(vinyl chloride) (PVC), poly(vinylidene fluoride-co-tetrafluoroethylene) (P(VDF-TFE)), and ultrahigh-molecular-weight poly(ethylene) (UHMWPE) with the subsequent GO reduction and composite hot pressing. A strong dependence of the segregated network polymer composites' physical properties on the polymer matrix was demonstrated. Particularly, 12 orders of magnitude rise of the polymers' electrical conductivity up to 0.7 S/m was found upon the incorporation of the reduced GO (rGO). A 17% increase in the P(VDF-TFE) elastic modulus filled by 1 wt % of rGO was observed. Fracture strength of PVC/rGO at 0.5 wt % content of the filler was demonstrated to decrease by fourfold. At the same time, the change in strength was not significant for P(VDF-TFE) and UHMWPE composites in comparison with pure polymers. Our results show a promise to accelerate the development of new composites for energy applications, such as metal-free supercapacitor plates and current collectors of lithium-ion batteries, bipolar plates of proton-exchange membrane fuel cells, antistatic elements of various electronic devices, etc. © 2020 American Chemical Society.
A Patternable and In Situ Formed Polymeric Zinc Blanket for a Reversible Zinc Anode in a Skin-Mountable Microbattery
2021, Zhu, Minshen, Hu, Junping, Lu, Qiongqiong, Dong, Haiyun, Karnaushenko, Dmitriy D., Becker, Christian, Karnaushenko, Daniil, Li, Yang, Tang, Hongmei, Qu, Zhe, Ge, Jin, Schmidt, Oliver G.
Owing to their high safety and reversibility, aqueous microbatteries using zinc anodes and an acid electrolyte have emerged as promising candidates for wearable electronics. However, a critical limitation that prevents implementing zinc chemistry at the microscale lies in its spontaneous corrosion in an acidic electrolyte that causes a capacity loss of 40% after a ten-hour rest. Widespread anti-corrosion techniques, such as polymer coating, often retard the kinetics of zinc plating/stripping and lack spatial control at the microscale. Here, a polyimide coating that resolves this dilemma is reported. The coating prevents corrosion and hence reduces the capacity loss of a standby microbattery to 10%. The coordination of carbonyl oxygen in the polyimide with zinc ions builds up over cycling, creating a zinc blanket that minimizes the concentration gradient through the electrode/electrolyte interface and thus allows for fast kinetics and low plating/stripping overpotential. The polyimide's patternable feature energizes microbatteries in both aqueous and hydrogel electrolytes, delivering a supercapacitor-level rate performance and 400 stable cycles in the hydrogel electrolyte. Moreover, the microbattery is able to be attached to human skin and offers strong resistance to deformations, splashing, and external shock. The skin-mountable microbattery demonstrates an excellent combination of anti-corrosion, reversibility, and durability in wearables. © 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH
High-Entropy Metal-Organic Frameworks for Highly Reversible Sodium Storage
2021, Ma, Yanjiao, Ma, Yuan, Dreyer, Sören Lukas, Wang, Qingsong, Wang, Kai, Goonetilleke, Damian, Omar, Ahmad, Mikhailova, Daria, Hahn, Horst, Breitung, Ben, Brezesinski, Torsten
Prussian blue analogues (PBAs) are reported to be efficient sodium storage materials because of the unique advantages of their metal-organic framework structure. However, the issues of low specific capacity and poor reversibility, caused by phase transitions during charge/discharge cycling, have thus far limited the applicability of these materials. Herein, a new approach is presented to substantially improve the electrochemical properties of PBAs by introducing high entropy into the crystal structure. To achieve this, five different metal species are introduced, sharing the same nitrogen-coordinated site, thereby increasing the configurational entropy of the system beyond 1.5R. By careful selection of the elements, high-entropy PBA (HE-PBA) presents a quasi-zero-strain reaction mechanism, resulting in increased cycling stability and rate capability. The key to such improvement lies in the high entropy and associated effects as well as the presence of several active redox centers. The gassing behavior of PBAs is also reported. Evolution of dimeric cyanogen due to oxidation of the cyanide ligands is detected, which can be attributed to the structural degradation of HE-PBA during battery operation. By optimizing the electrochemical window, a Coulombic efficiency of nearly 100% is retained after cycling for more than 3000 cycles.
Mechanical Characterization of Compact Rolled-up Microtubes Using In Situ Scanning Electron Microscopy Nanoindentation and Finite Element Analysis
2021, Moradi, Somayeh, Jöhrmann, Nathanael, Karnaushenko, Dmitriy D., Zschenderlein, Uwe, Karnaushenko, Daniil, Wunderle, Bernhard, Schmidt, Oliver G.
Self-assembled Swiss-roll microstructures (SRMs) are widely explored to build up microelectronic devices such as capacitors, transistors, or inductors as well as sensors and lab-in-a-tube systems. These devices often need to be transferred to a special position on a microchip or printed circuit board for the final application. Such a device transfer is typically conducted by a pick-and-place process exerting enormous mechanical loads onto the 3D components that may cause catastrophic failure of the device. Herein, the mechanical deformation behavior of SRMs using experiments and simulations is investigated. SRMs using in situ scanning electron microscopy (SEM) combined with nanoindentation are characterized. This allows us to mimic and characterize mechanical loads as they occur in a pick-and-place process. The deformation response of SRMs depends on three geometrical factors, i.e., the number of windings, compactness of consecutive windings, and inner diameter of the microtube. Nonlinear finite element analysis (FEA) showing good agreement with experiments is performed. It is believed that the insights into the mechanical loading of 3D self-assembled architectures will lead to novel techniques suitable for a new generation of pick-and-place machines operating at the microscale. © 2021 The Authors. Advanced Engineering Materials published by Wiley-VCH GmbH
2D/3D Metallic Nano-objects Self-Organized in an Organic Molecular Thin Film
2020, Molodtsova, Olga V., Aristova, Irina M., Potorochin, Dmitrii V., Babenkov, Sergey V., Khodos, Igor I., Molodtsov, Serguei L., Makarova, Anna A., Smirnov, Dmitry A., Aristov, Victor Yu.
We present the fabrication and investigation of the properties of nanocomposite structures consisting of two-dimensional (2D) and three-dimensional (3D) metallic nano-objects self-organized on the surface and inside of organic molecular thin-film copper tetrafluorophthalocyanine (CuPcF4). Metallic atoms, deposited under ultrahigh vacuum (UHV) conditions onto the organic ultrathin film, diffuse along the surface and self-assemble into a system of 2D metallic overlayers. At the same time, the majority of the metal atoms diffuse into the organic matrix and self-organize into 3D nanoparticles (NPs) in a well-defined manner. The evolution of the morphology and electronic properties of such structures as a function of nominal metal content is studied under UHV conditions using transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM), and photoelectron spectroscopy (PES) techniques. Using HR-TEM, we have observed the periodicity of atomic planes of individual silver NPs. The steady formation of agglomerates from individual single nanocrystallites with intercrystallite boundaries is observed as well. PES reveals generally weak chemical interactions between silver and the organic matrix and n-doping of CuPcF4 at the initial stages of silver deposition, which is associated with charge transfer from the 2D wetting layer on the basis of core-level spectra shift analysis. Copyright © 2020 American Chemical Society.
Digital Electrochemistry for On-Chip Heterogeneous Material Integration
2021, Bao, Bin, Rivkin, Boris, Akbar, Farzin, Karnaushenko, Dmitriy D., Bandari, Vineeth Kumar, Teuerle, Laura, Becker, Christian, Baunack, Stefan, Karnaushenko, Daniil, Schmidt, Oliver G.
Many modern electronic applications rely on functional units arranged in an active-matrix integrated on a single chip. The active-matrix allows numerous identical device pixels to be addressed within a single system. However, next-generation electronics requires heterogeneous integration of dissimilar devices, where sensors, actuators, and display pixels sense and interact with the local environment. Heterogeneous material integration allows the reduction of size, increase of functionality, and enhancement of performance; however, it is challenging since front-end fabrication technologies in microelectronics put extremely high demands on materials, fabrication protocols, and processing environments. To overcome the obstacle in heterogeneous material integration, digital electrochemistry is explored here, which site-selectively carries out electrochemical processes to deposit and address electroactive materials within the pixel array. More specifically, an amorphous indium-gallium-zinc oxide (a-IGZO) thin-film-transistor (TFT) active-matrix is used to address pixels within the matrix and locally control electrochemical reactions for material growth and actuation. The digital electrochemistry procedure is studied in-depth by using polypyrrole (PPy) as a model material. Active-matrix-driven multicolored electrochromic patterns and actuator arrays are fabricated to demonstrate the capabilities of this approach for material integration. The approach can be extended to a broad range of materials and structures, opening up a new path for advanced heterogeneous microsystem integration.
Signatures of Sixfold Degenerate Exotic Fermions in a Superconducting Metal PdSb2
2020, Kumar, Nitesh, Yao, Mengyu, Nayak, Jayita, Vergniory, Maia G., Bannies, Jörn, Wang, Zhijun, Schröter, Niels B.M., Strocov, Vladimir N., Müchler, Lukas, Shi, Wujun, Rienks, Emile D.L., Mañes, J.L., Shekhar, Chandra, Parkin, Stuart S.P., Fink, Jörg, Fecher, Gerhard H., Sun, Yan, Bernevig, B. Andrei, Felser, Claudia
Multifold degenerate points in the electronic structure of metals lead to exotic behaviors. These range from twofold and fourfold degenerate Weyl and Dirac points, respectively, to sixfold and eightfold degenerate points that are predicted to give rise, under modest magnetic fields or strain, to topological semimetallic behaviors. The present study shows that the nonsymmorphic compound PdSb2 hosts six-component fermions or sextuplets. Using angle-resolved photoemission spectroscopy, crossing points formed by three twofold degenerate parabolic bands are directly observed at the corner of the Brillouin zone. The group theory analysis proves that under weak spin–orbit interaction, a band inversion occurs. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
A High-Voltage, Dendrite-Free, and Durable Zn–Graphite Battery
2019, Wang, Gang, Kohn, Benjamin, Scheler, Ulrich, Wang, Faxing, Oswald, Steffen, Löffler, Markus, Tan, Deming, Zhang, Panpan, Zhang, Jian, Feng, Xinliang
The intrinsic advantages of metallic Zn, like high theoretical capacity (820 mAh g−1), high abundance, low toxicity, and high safety have driven the recent booming development of rechargeable Zn batteries. However, the lack of high-voltage electrolyte and cathode materials restricts the cell voltage mostly to below 2 V. Moreover, dendrite formation and the poor rechargeability of the Zn anode hinder the long-term operation of Zn batteries. Here a high-voltage and durable Zn–graphite battery, which is enabled by a LiPF6-containing hybrid electrolyte, is reported. The presence of LiPF6 efficiently suppresses the anodic oxidation of Zn electrolyte and leads to a super-wide electrochemical stability window of 4 V (vs Zn/Zn2+). Both dendrite-free Zn plating/stripping and reversible dual-anion intercalation into the graphite cathode are realized in the hybrid electrolyte. The resultant Zn–graphite battery performs stably at a high voltage of 2.8 V with a record midpoint discharge voltage of 2.2 V. After 2000 cycles at a high charge–discharge rate, high capacity retention of 97.5% is achieved with ≈100% Coulombic efficiency. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Interfacial Covalent Bonds Regulated Electron-Deficient 2D Black Phosphorus for Electrocatalytic Oxygen Reactions
2021, Wang, Xia, Raghupathy, Ramya Kormath Madam, Querebillo, Christine Joy, Liao, Zhongquan, Li, Dongqi, Lin, Kui, Hantusch, Martin, Sofer, Zdeněk, Li, Baohua, Zschech, Ehrenfried, Weidinger, Inez M., Kühne, Thomas D., Mirhosseini, Hossein, Yu, Minghao, Feng, Xinliang
Developing resource-abundant and sustainable metal-free bifunctional oxygen electrocatalysts is essential for the practical application of zinc–air batteries (ZABs). 2D black phosphorus (BP) with fully exposed atoms and active lone pair electrons can be promising for oxygen electrocatalysts, which, however, suffers from low catalytic activity and poor electrochemical stability. Herein, guided by density functional theory (DFT) calculations, an efficient metal-free electrocatalyst is demonstrated via covalently bonding BP nanosheets with graphitic carbon nitride (denoted BP-CN-c). The polarized P-N covalent bonds in BP-CN-c can efficiently regulate the electron transfer from BP to graphitic carbon nitride and significantly promote the OOH* adsorption on phosphorus atoms. Impressively, the oxygen evolution reaction performance of BP-CN-c (overpotential of 350 mV at 10 mA cm−2, 90% retention after 10 h operation) represents the state-of-the-art among the reported BP-based metal-free catalysts. Additionally, BP-CN-c exhibits a small half-wave overpotential of 390 mV for oxygen reduction reaction, representing the first bifunctional BP-based metal-free oxygen catalyst. Moreover, ZABs are assembled incorporating BP-CN-c cathodes, delivering a substantially higher peak power density (168.3 mW cm−2) than the Pt/C+RuO2-based ZABs (101.3 mW cm−2). The acquired insights into interfacial covalent bonds pave the way for the rational design of new and affordable metal-free catalysts. © 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH
Calciothermic Synthesis of Very Fine, Hydrogenated Ti and Ti–Nb Powder for Biomedical Applications
2020, Lindemann, Inge, Gebel, Bernhard, Pilz, Stefan, Uhlemann, Margitta, Gebert, Annett
Due to their excellent biocompatibility, titanium and titanium–niobium alloys are especially interesting for biomedical applications. With regard to favorable near-net shape production, Ti powder synthesis is the key hurdle. Extensive research has been in progress for alternative synthesis methods since decades. Herein, an efficient alternative method to the conventional powder production process to prepare spherical powders with very small sizes (<45 μm) for high-strength materials is shown. Very fine, hydrogenated Ti and Ti–Nb alloy powders are stable in air and are synthesized by calciothermic reduction in hydrogen. The herein presented reduction using CaH2 starts directly from the oxides instead of chlorides. Correlations of size and morphology of the as-synthesized TiH2 and (Ti,Nb)H2 powders with the precursors (TiO2, Nb2O5, and CaH2) are illustrated and are used to tailor the desired powders.