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Auger- and X-ray Photoelectron Spectroscopy at Metallic Li Material: Chemical Shifts Related to Sample Preparation, Gas Atmosphere, and Ion and Electron Beam Effects
Li-based batteries are a key element in reaching a sustainable energy economy in the near future. The understanding of the very complex electrochemical processes is necessary for the optimization of their performance. X-ray photoelectron spectroscopy (XPS) is an accepted method used to improve understanding around the chemical processes at the electrode surfaces. Nevertheless, its application is limited because the surfaces under investigation are mostly rough and inhomogeneous. Local elemental analysis, such as Auger electron spectroscopy (AES), could assist XPS to gain more insight into the chemical processes at the surfaces. In this paper, some challenges in using electron spectroscopy are discussed, such as binding energy (BE) referencing for the quantitative study of chemical shifts, gas atmospheric influences, or beam damage (including both AE and XP spectroscopy). Carefully prepared and surface-modified metallic lithium material is used as model surface, considering that Li is the key element for most battery applications.
Structural and Electrochemical Properties of Layered P2-Na0.8Co0.8Ti0.2O2 Cathode in Sodium-Ion Batteries
Layered Na0.8Co0.8Ti0.2O2 oxide crystallizes in the β-RbScO2 structure type (P2 modification) with Co(III) and Ti(IV) cations sharing the same crystallographic site in the metal-oxygen layers. It was synthesized as a single-phase material and characterized as a cathode in Na- and Na-ion batteries. A reversible capacity of about 110 mA h g−1 was obtained during cycling between 4.2 and 1.8 V vs. Na+/Na with a 0.1 C current density. This potential window corresponds to minor structural changes during (de)sodiation, evaluated from operando XRD analysis. This finding is in contrast to Ti-free NaxCoO2 materials showing a multi-step reaction mechanism, thus identifying Ti as a structure stabilizer, similar to other layered O3- and P2-NaxCo1−yTiyO2 oxides. However, charging the battery with the Na0.8Co0.8Ti0.2O2 cathode above 4.2 V results in the reversible formation of a O2-phase, while discharging below 1.5 V leads to the appearance of a second P2-layered phase with a larger unit cell, which disappears completely during subsequent battery charge. Extension of the potential window to higher or lower potentials beyond the 4.2–1.8 V range leads to a faster deterioration of the electrochemical performance. After 100 charging-discharging cycles between 4.2 and 1.8 V, the battery showed a capacity loss of about 20% in a conventional carbonate-based electrolyte. In order to improve the cycling stability, different approaches including protective coatings or layers of the cathodic and anodic surface were applied and compared with each other.
Progress and challenges in using sustainable carbon anodes in rechargeable metal-ion batteries
Rechargeable lithium-ion batteries (LIBs) are one of the most promising alternatives to effectively bypass fossil fuels. However, long-term energy application of LIBs could be restricted in the future due to the increased production cost of LIB arising from the shortage and inaccessibility of Li in the Earth's crust. Na or K have been considered as substitutes for Li but in spite of their natural abundance, they suffer from low gravimetric/volumetric energy density. An alternative to increase the efficiency of sodium-ion battery (SIBs) and potassium-ion battery (KIBs) is to focus on finding the high‐performing negative electrode, the anode. The large volume changes of alloying and conversion type anodes for KIBs and SIBs make hard carbons to a better option on this regard than usual graphitic carbons, but a key obstacle is the reliance on unsustainable sources. Thus, biomass-derived carbon could offer a promising alternative, and it has indeed been in the focus of much recent work. This review highlights the recent advances in using carbon extracted from various biomass sources in rechargeable Li-, Na-, and K-ion batteries. Maximizing the energy and power densities as well as the lifetime of carbon anodes require an exploration of the right balance between carbon structures, pore morphology, chemical composition and alkali metal-ion storage. Thus, in this review, first, we take stock of key challenges and opportunities to extract carbon from various plants structural components and identify the extracted carbon structure compared to graphite-like structure. Then, we provide an overview on morphological and structural modification of the extracted carbons. Finally, we show how the physicochemical properties, structural alignment and morphological variation of the biomass-derived carbon can affect the storage mechanism and electrochemical performance. The extensive overview of this topic provided here is expected to stimulate further work on environmentally friendly battery design and towards the optimization of the battery performance. Electrode materials in alkali-metal-ion batteries that are based on biomass-derived carbon may allow not only a technical breakthrough, but also an ethically and socially acceptable product.
Applications of nanogenerators for biomedical engineering and healthcare systems
The dream of human beings for long living has stimulated the rapid development of biomedical and healthcare equipment. However, conventional biomedical and healthcare devices have shortcomings such as short service life, large equipment size, and high potential safety hazards. Indeed, the power supply for conventional implantable device remains predominantly batteries. The emerging nanogenerators, which harvest micro/nanomechanical energy and thermal energy from human beings and convert into electrical energy, provide an ideal solution for self‐powering of biomedical devices. The combination of nanogenerators and biomedicine has been accelerating the development of self‐powered biomedical equipment. This article first introduces the operating principle of nanogenerators and then reviews the progress of nanogenerators in biomedical applications, including power supply, smart sensing, and effective treatment. Besides, the microbial disinfection and biodegradation performances of nanogenerators have been updated. Next, the protection devices have been discussed such as face mask with air filtering function together with real‐time monitoring of human health from the respiration and heat emission. Besides, the nanogenerator devices have been categorized by the types of mechanical energy from human beings, such as the body movement, tissue and organ activities, energy from chemical reactions, and gravitational potential energy. Eventually, the challenges and future opportunities in the applications of nanogenerators are delivered in the conclusive remarks. The combination of nanogenerator and biomedicine have been accelerating the development of self‐powered biomedical devices, which show a bright future in biomedicine and healthcare such as smart sensing, and therapy.
Active Matrix Flexible Sensory Systems: Materials, Design, Fabrication, and Integration
A variety of modern applications including soft robotics, prosthetics, and health monitoring devices that cover electronic skins (e-skins), wearables as well as implants have been developed within the last two decades to bridge the gap between artificial and biological systems. During this development, high-density integration of various sensing modalities into flexible electronic devices becomes vitally important to improve the perception and interaction of the human bodies and robotic appliances with external environment. As a key component in flexible electronics, the flexible thin-film transistors (TFTs) have seen significant advances, allowing for building flexible active matrices. The flexible active matrices have been integrated with distributed arrays of sensing elements, enabling the detection of signals over a large area. The integration of sensors within pixels of flexible active matrices has brought the application scenarios to a higher level of sophistication with many advanced functionalities. Herein, recent progress in the active matrix flexible sensory systems is reviewed. The materials used to construct the semiconductor channels, the dielectric layers, and the flexible substrates for the active matrices are summarized. The pixel designs and fabrication strategies for the active matrix flexible sensory systems are briefly discussed. The applications of the flexible sensory systems are exemplified by reviewing pressure sensors, temperature sensors, photodetectors, magnetic sensors, and biosignal sensors. At the end, the recent development is summarized and the vision on the further advances of flexible active matrix sensory systems is provided.
Small Scale Propulsion: How Systematic Studies of Low Reynolds Number Physics Can Bring Micro/Nanomachines to New Horizons
Micromachines are small-scale human-made machines with remarkable potential for medical treatments, microrobotics and environmental remediation applications. However, meaningful real-world applications are missing. This is mainly caused by their small size leading to unintuitive physics of motion. Motivated by the aim of understanding the fundamental physics at the micrometer scale and thereby overcoming resulting challenges, we discuss the importance of robust models supported by experimental data. Our previously performed study on the switching in propulsion mechanisms for conical tubular catalytic micromotors will be summarized and serve as an example for discussion. We emphasize on the need for systematic experimental studies to enable the design of highly application-oriented micromachines, which can be translated into real-world scenarios.
Insights into the Spin–Orbital Entanglement in Complex Iridium Oxides from High-Field ESR Spectroscopy
Complex iridium oxides have attracted recently a substantial interdisciplinary attention due to an intimate entanglement of spin and orbital degrees of freedom which may give rise to a novel spin–orbital Mott insulating behavior and exotic quantum spin liquid phases. Electron spin resonance (ESR) spectroscopy is known to be an instructive tool for studying the spin–orbital coupling (SOC) effects as it can directly access the relevant parameters sensitive to SOC, such as the g factor tensor, magnetic anisotropy gaps and spin dynamics. In this article, a systematic study at the Leibniz IFW Dresden of the static and dynamic properties of selected Ir-based materials with multi-frequency high-field ESR spectroscopy will be reviewed. Specifically, evidence for a surprisingly isotropic antiferromagnetic spin dynamics and the inversion of the orbital states in the prototypical spin–orbital Mott insulator Sr 2IrO 4, observation of the collective resonance modes in the family of double perovskites La 2BIrO 6 (B = Cu, Co) and the origin of the unexpected magnetism in the double perovskite Ba 2YIrO 6 will be highlighted. © 2021, The Author(s).
Tailoring Plasmonics of Au@Ag Nanoparticles by Silica Encapsulation
Hybrid metallic nanoparticles (NPs) encapsulated in oxide shells are currently intensely studied for plasmonic applications in sensing, medicine, catalysis, and photovoltaics. Here, a method for the synthesis of Au@Ag@SiO2 cubes with a uniform silica shell of variable and adjustable thickness in the nanometer range is introduced and their excellent, highly reproducible, and tunable optical response is demonstrated. Varying the silica shell thickness, the excitation energies of the single NP plasmon modes can be tuned in a broad spectral range between 2.55 and 3.25 eV. Most importantly, a strong coherent coupling of the surface plasmons is revealed at the silver–silica interface with Mie resonances at the silica–vacuum interface leading to a significant field enhancement at the encapsulated NP surface in the range of 100% at shell thicknesses t ≃ 20 nm. Consequently, the synthesis method and the field enhancement open pathways to a widespread use of silver NPs in plasmonic applications including photonic crystals and may be transferred to other non-precious metals. © 2021 The Authors. Advanced Optical Materials published by Wiley-VCH GmbH
Towards Green 3D-Microfabrication of Bio-MEMS Devices Using ADEX Dry Film Photoresists
Current trends in miniaturized diagnostics indicate an increasing demand for large quantities of mobile devices for health monitoring and point-of-care diagnostics. This comes along with a need for rapid but preferably also green microfabrication. Dry film photoresists (DFPs) promise low-cost and greener microfabrication and can partly or fully replace conventional silicon-technologies being associated with high-energy demands and the intense use of toxic and climate-active chemicals. Due to their mechanical stability and superior film thickness homogeneity, DFPs outperform conventional spin-on photoresists, such as SU-8, especially when three-dimensional architectures are required for micro-analytical devices (e.g. microfluidics). In this study, we utilize the commercial epoxy-based DFP ADEX to demonstrate various application scenarios ranging from the direct modification of microcantilever beams via the assembly of microfluidic channels to lamination-free patterning of DFPs, which employs the DFP directly as a substrate material. Finally, kinked, bottom-up grown silicon nanowires were integrated in this manner as prospective ion-sensitive field-effect transistors in a bio-probe architecture directly on ADEX substrates. Hence, we have developed the required set of microfabrication protocols for such an assembly comprising metal thin film deposition, direct burn-in of lithography alignment markers, and polymer patterning on top of the DFP.
All-on-Chip Concurrent Measurements of the Static Magnetization and of the Electron Spin Resonance with Microcantilevers
A large variety of the samples of novel magnetic materials, which are of high interest due to their exotic properties, are only available in very small sizes. In some cases, it is not possible to synthesize large single crystals; in other cases, the small size itself is the key prerequisite to manifest a specifically interesting property of the material. The smallness of a sample rises a problem of the detection of the static magnetic response and of the electron spin resonance (ESR) signal. To overcome this problem, we propose to use a cantilever-based (torque-detected) setup with the capability of a simultaneous measurement of ESR and static magnetization. This setup offers a high sensitivity and the ability to acquire along with the ESR signal the components of the magnetization tensor in a single experimental run. Here, we present the working principle of this setup, as well as the estimate of its sensitivity from the measurements on the standard Co Tutton salt sample. © 2021, The Author(s).