Highly Stretchable Microsupercapacitor Arrays with Honeycomb Structures for Integrated Wearable Electronic Systems

The rapid development of portable and wearable electronics has greatly increased the demand for energy storage devices with similar physical properties and integration capability. This paper introduces a honeycomb polydimethylsiloxane substrate for stretchable microsupercapacitor (MSC) arrays, which enables facile integration with other electronics. The honeycomb structure can accommodate a large deformation without producing excessive strain in the MSCs and interconnects. The results of this study show that such stretchable MSC arrays with single-walled carbon nanotube electrodes demonstrate excellent rate capability and power performance as well as electrochemical stability up to 150% (zero prestrain) or 275% (−50% prestrain) stretching and under excessive bending or twisting. The present stretchable MSC arrays with honeycomb structures show high potential for integration with other electronics, such as energy harvesters, power management circuits, wireless charging circuits, and various sensors, encompassing a wide range of wearable, bioimplantable electronic systems

Engineering the Microstructure of Electrospun Fibrous Scaffolds by Microtopography

Controlling the structure and organization of electrospun fibers is desirable for fabricating scaffolds and materials with defined microstructures. However, the effects of microtopography on the deposition and, in turn, the organization of the electrospun fibers are not well understood. In this study, conductive polydimethylsiloxane (PDMS) templates with different micropatterns were fabricated by combining photolithography, silicon wet etching, and PDMS molding techniques. The fiber organization was varied by fine-tuning the microtopography of the electrospinning collector. Fiber conformity and alignment were influenced by the depth and the slope of microtopography features, resulting in scaffolds comprising either an array of microdomains with different porosity and fiber alignment or an array of microwells. Microtopography affected the fiber organization for hundreds of micrometers below the scaffold surface, resulting in scaffolds with distinct surface properties on each side. In addition, the fiber diameter was also affected by the fiber conformity. The effects of the fiber arrangement in the scaffolds on the morphology, migration, and infiltration of cells were examined by in vitro and in vivo experiments. Cell morphology and organization were guided by the fibers in the microdomains, and cell migration was enhanced by the aligned fibers and the three-dimensional scaffold structure. Cell infiltration was correlated with the microdomain porosity. Microscale control of the fiber organization and the porosity at the surface and through the thickness of the fibrous scaffolds, as demonstrated by the results of this study, provides a powerful means of engineering the three-dimensional structure of electrospun fibrous scaffolds for cell and tissue engineering

The Chemistry of Electrolyte Reduction on Silicon Electrodes Revealed by <i>in Situ</i> ATR-FTIR Spectroscopy

While silicon is the most promising next-generation anode material for lithium-ion batteries (LIBs), silicon electrodes exhibit significant capacity fade with cycling. A common hypothesis is that the capacity loss is due to the solid electrolyte interphase (SEI) forming in the first cycle and becoming destabilized by large cyclic volume changes. A cell for <i>in situ</i> attenuated total reflection-Fourier transform infrared spectroscopy with controllable penetration depth was used to study the chemistry at the electrode–electrolyte interface. The SEI product precursors at the interface were successfully identified and differentiated from free or solvated solvent molecules in the bulk electrolyte. Intriguingly, for the most common electrolyte consisting of ethylene carbonate and diethyl carbonate, ethylene carbonate was found to directly reduce to lithium ethylene dicarbonate on the lithiated silicon surface and diethyl carbonate to selectively reduce to diethyl 2,5-dioxa­hexane dicarboxylate on the surface of the native silicon-oxide film. Understanding this surface dependence of the SEI composition is critical to tuning the silicon electrode surface condition and, ultimately, enhancing the performance of future LIBs

Structure Sensitivity in Pt Nanoparticle Catalysts for Hydrogenation of 1,3-Butadiene: <i>In Situ</i> Study of Reaction Intermediates Using SFG Vibrational Spectroscopy

The product selectivity during 1,3-butadiene hydrogenation on monodisperse, colloidally synthesized, Pt nanoparticles was studied under reaction conditions with kinetic measurements and <i>in situ</i> sum frequency generation (SFG) vibrational spectroscopy. SFG was performed with the capping ligands intact in order to maintain nanoparticle size by reduced sintering. Four products are formed at 75 °C: 1-butene, <i>cis</i>-2-butene, <i>trans</i>-2-butene, and <i>n-</i>butane. Ensembles of Pt nanoparticles with average diameters of 0.9 and 1.8 nm exhibit a ∼30% and ∼20% increase in the full hydrogenation products, respectively, as compared to Pt nanoparticles with average diameters of 4.6 and 6.7 nm. Methyl and methylene vibrational stretches of reaction intermediates observed under working conditions using SFG were used to correlate the stable reaction intermediates with the product distribution. Kinetic and SFG results correlate with previous DFT predictions for two parallel reaction pathways of 1,3-butadiene hydrogenation. Hydrogenation of 1,3-butadiene can initiate with H-addition at internal or terminal carbons leading to the formation of 1-buten-4-yl radical (metallocycle) and 2-buten-1-yl radical intermediates, respectively. Small (0.9 and 1.8 nm) nanoparticles exhibited vibrational resonances originating from both intermediates, while the large (4.6 and 6.7 nm) particles exhibited vibrational resonances originating predominately from the 2-buten-1-yl radical. This suggests each reaction pathway competes for partial and full hydrogenation and the nanoparticle size affects the kinetic preference for the two pathways. The reaction pathway through the metallocycle intermediate on the small nanoparticles is likely due to the presence of low-coordinated sites

A Catalytic Path for Electrolyte Reduction in Lithium-Ion Cells Revealed by <i>in Situ</i> Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy

Although controlling the interfacial chemistry of electrodes in Li-ion batteries (LIBs) is crucial for maintaining the reversibility, electrolyte decomposition has not been fully understood. In this study, electrolyte decomposition on model electrode surfaces (Au and Sn) was investigated by <i>in situ</i> attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. Simultaneously obtained ATR-FTIR spectra and cyclic voltammetry measurements show that lithium ethylene dicarbonate and lithium propionate form on the Au electrode at 0.6 V, whereas diethyl 2,5-dioxahexane dicarboxylate and lithium propionate form on the Sn electrode surface at 1.25 V. A noncatalytic reduction path on the Au surface and a catalytic reduction path on the Sn surface are introduced to explain the surface dependence of the overpotential and product selectivity. This represents a new concept for explaining electrolyte reactions on the anode of LIBs. The present investigation shows that catalysis plays a dominant role in the electrolyte decomposition process and has important implications in electrode surface modification and electrolyte recipe selection, which are critical factors for enhancing the efficiency, durability, and reliability of LIBs

Sum Frequency Generation Vibrational Spectroscopy of 1,3-Butadiene Hydrogenation on 4 nm Pt@SiO₂, Pd@SiO₂, and Rh@SiO₂ Core–Shell Catalysts

1,3-Butadiene (1,3-BD) hydrogenation was performed on 4 nm Pt, Pd, and Rh nanoparticles (NPs) encapsulated in SiO₂ shells at 20, 60, and 100 °C. The core–shells were grown around polyvinylpyrrolidone (PVP) coated NPs (Stöber encapsulation) prepared by colloidal synthesis. Sum frequency generation (SFG) vibrational spectroscopy was performed to correlate surface intermediates observed in situ with reaction selectivity. It is shown that calcination is effective in removing PVP, and the SFG signal can be generated from the metal surface. Using SFG, it is possible to compare the surface vibrational spectrum of Pt@SiO₂ (1,3-BD is hydrogenated through multiple paths and produces butane, 1-butene, and <i>cis</i>/<i>trans</i>-2-butene) to Pd@SiO₂ (1,3-BD favors one path and produces 1-butene and <i>cis</i>/<i>trans</i>-2-butene). In contrast to Pt@SiO₂ and Pd@SiO₂, SFG and kinetic experiments of Rh@SiO₂ show a permanent accumulation of organic material