Ti 3 C 2 T x belongs to the family of MXenes, 2D materials with an attractive combination of functional properties suitable for applications such as batteries, supercapacitors, and strain sensors. However, the fabrication of devices and functional coatings based on Ti 3 C 2 T x remains challenging as they are prone to chemical degradation by their oxidation to TiO 2. In this paper, we examine the oxidation of Ti 3 C 2 T x in air, liquid, and solid media via conductivity measurements to assess the shelf life of Ti 3 C 2 T x MXenes. The oxidation of Ti 3 C 2 T x was observed in all the media used in this study, but it is fastest in liquid media and slowest in solid media (including polymer matrices). We also show that the conventional indicators of MXene oxidation, such as changes in color and colloidal stability, are not always reliable. Finally, we demonstrate the acceleration of oxidation under exposure to UV light.
Bendable, stretchable MXene multilayer coatings are deposited onto a wide variety of surfaces, rendering them conductive and responsive.
Inkjet-printable aqueous suspensions of conjugated polymer precursors are developed for fabrication of patterned color images on paper substrates. Printing of a diacetylene (DA)-surfactant composite ink on unmodified paper and photopaper, as well as on a banknote, enables generation of latent images that are transformed to blue-colored polydiacetylene (PDA) structures by UV irradiation. Both irreversible and reversible thermochromism with the PDA printed images are demonstrated and applied to flexible and disposable sensors and to displays.
The rapidly growing fields of noncontact medical diagnosis, noninvasive epidermal sensing, and environmental monitoring bring forward the need for fast humidity sensors. However, achieving a rapid response to dynamic changes in humidity, such as for human respiration, is challenging. This is because the response can be limited by the diffusion of water, the sorption of water in the material, and the sensing method itself. Here, the water sorption and response mechanism for multilayer assemblies made from MXene nanosheets and polyelectrolytes for ultrafast humidity sensing are described. MXenes are a class of two-dimensional transition metal carbides (e.g., Ti 3 C 2 ) possessing hydrophilicity and metal-like conductivity. Herein we show that MXene/polyelectrolyte multilayer films prepared using layer-by-layer (LbL) assembly exhibit response and recovery times exceeding those of most humidity sensors. Quartz crystal microbalance and ellipsometry support the mechanism that, upon changing humidity, water molecules intercalate into (or deintercalate from) the MXene/polyelectrolyte multilayer, resulting in an increase (or a decrease) in the thickness and sheet-to-sheet distance, which then changes the tunneling resistance between MXene sheets. The ultrafast response was further demonstrated by monitoring real-time human respiration using a portable microcontroller for wireless sensing.
As they have been designed to undergo colorimetric changes that are dependent on the polarity of solvents, the majority of conventional solvatochromic molecule based sensor systems inevitably display broad overlaps in their absorption and emission bands. As a result, colorimetric differentiation of solvents of similar polarity has been extremely difficult. Here we present a tailor-made colorimetric and fluorescence turn-on type solvatochromic sensor that enables facile identification of a specific solvent. The sensor system displays a colorimetric transition only when a thin protective layer, which protects the solvatochromic materials, is destroyed or disrupted by a specific solvent. The versatility of the strategy is demonstrated by designing a sensor that differentiates chloroform and dichloromethane colorimetrically and one that performs sequence selective colorimetric sensing. In addition, the approach is employed to construct a solvatochromic molecular AND logic gate. The new strategy could open new avenues for the development of novel solvatochromic sensors.
Nanostructure-forming polymers have tremendous potential to enhance the performance and safety of lithium-ion batteries (LiBs) as a result of their ability to simultaneously optimize often contradictory properties, such as ionic conductivity and mechanical stability, in a single material. These macromolecules can be harnessed in both LiB electrolyte and electrode components. With respect to electrolytes, advances in salt-doped and single-ion systems are highlighted herein with a focus on strategies that improve conductivities to rival that found in gel and liquid electrolytes, while also permitting further enhancements in electrochemical and mechanical stability. In the arena of electrodes, three major functions are considered: binders to maximize active material efficiency, polymer electrodes to enable fully organic LiBs, and sacrificial constructs that template high surface area, well-ordered metal oxide or metallic electrodes to improve electrode capacity. Additionally, the application of theory and simulation to streamline the development of key structure–property−processing relationships in ion-conducting nanomaterials is discussed. Finally, several next steps and future directions are suggested to accelerate the fabrication of next-generation LiBs.
An understanding of how complex nanoscale morphologies emerge from synthesis would offer powerful strategies to construct soft materials with designed structures and functions. However, these kinds of morphologies have proven difficult to characterize, and therefore manipulate, because they are three-dimensional (3D), nanoscopic, and often highly irregular. Here, we studied polyamide (PA) membranes used in wastewater reclamation as a prime example of this challenge. Using electron tomography and quantitative morphometry, we reconstructed the nanoscale morphology of 3D crumples and voids in PA membranes for the first time. Various parameters governing film transport properties, such as surface-to-volume ratio and mass-per-area, were measured directly from the reconstructed membrane structure. In addition, we extracted information inaccessible by other means. For example, 3D reconstruction shows that membrane nanostructures are formed from PA layers 15–20 nm thick folding into 3D crumples which envelope up to 30% void by volume. Mapping local curvature and thickness in 3D quantitatively groups these crumples into three classes, “domes”, “dimples”, and “clusters”, each being a distinct type of microenvironment. Elemental mapping of metal ion adsorption across the film demonstrates that these previously missed parameters are relevant to membrane performance. This imaging–morphometry platform can be applicable to other nanoscale soft materials and potentially suggests engineering strategies based directly on synthesis–morphology–function relationships.
An emergent theme in mono-and multivalent ion batteries is to utilize nanoparticles (NPs) as electrode materials based on the phenomenological observations that their short ion diffusion length and large electrode−electrolyte interface can lead to improved ion insertion kinetics compared to their bulk counterparts. However, the understanding of how the NP size fundamentally relates to their electrochemical behaviors (e.g., charge storage mechanism, phase transition associated with ion insertion) is still primitive. Here, we employ spinel λ-MnO 2 particles as a model cathode material, which have effective Mg 2+ ion intercalation but with their size effect poorly understood to investigate their operating mechanism via a suite of electrochemical and structural characterizations. We prepare two differently sized samples, the small nanoscopic λ-MnO 2 particles (81 ± 25 nm) and big micron-sized ones (814 ± 207 nm) via postsynthesis size-selection. Analysis of the charge storage mechanisms shows that the stored charge from Mg 2+ ion intercalation dominates in both systems and is ∼10 times higher in small particles than that in the big ones. From both X-ray diffraction and atomic-resolution scanning transmission electron microscopy imaging, we reveal a fundamental difference in phase transition of the differently sized particles during Mg 2+ ion intercalation: the small NPs undergo a solid-solution-like phase transition which minimizes lattice mismatch and energy penalty for accommodating new phases, whereas the big particles follow conventional multiphase transformation. We show that this pathway difference is related to the improved electrochemical performance (e.g., rate capability, cycling performance) of small particles over the big ones which provides important insights in encoding within the particle dimension, that is, the single-phase transition pathway in high-performance electrode materials for multivalent ion batteries.
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