Ternary Eutectic Electrolyte-Assisted Formation and Dynamic Breathing Effect of the Solid-Electrolyte Interphase for High-Stability Aqueous Magnesium-Ion Full Batteries.

Aqueous rechargeable magnesium batteries hold immense potential for intrinsically safe, cost-effective, and sustainable energy storage. However, their viability is constrained by a narrow voltage range and suboptimal compatibility between the electrolyte and electrodes. Herein, we introduce an innovative ternary deep eutectic Mg-ion electrolyte composed of MgCl2·6H2O, acetamide, and urea in a precisely balanced 1:1:7 molar ratio. This formulation was optimized by leveraging competitive solvation effects between Mg2+ ions and two organic components. The full batteries based on this ternary eutectic electrolyte, Mn-doped sodium vanadate (Mn-NVO) anode, and copper hexacyanoferrate cathode exhibited an elevated voltage plateau and high rate capability and showcased stable cycling performance. Ex-situ characterizations unveiled the Mg2+ storage mechanism of Mn-NVO involving initial extraction of Na+ followed by subsequent Mg2+ intercalation/deintercalation. Detailed spectroscopic analyses illuminated the formation of a pivotal solid-electrolyte interphase on the anode surface. Moreover, the solid-electrolyte interphase demonstrated a dynamic adsorption/desorption behavior, referred to as the "breathing effect", which substantially mitigated undesired dissolution and side reactions of electrode materials. These findings underscore the crucial role of rational electrolyte design in fostering the development of a favorable solid-electrolyte interphase that can significantly enhance compatibility between electrode materials and electrolytes, thus propelling advancements in aqueous multivalent-ion batteries.

Quadruple H-Bonding and Polyrotaxanes Dual Cross-linking Supramolecular Elastomer for High Toughness and Self-healing Conductors.

Tough and self-healable substrates can enable stretchable electronics long service life. However, for substrates, it still remains a challenge to achieve both high toughness and autonomous self-healing ability at room temperature. Herein, a strategy by using the combined effects between quadruple H-bonding and slidable cross-links is proposed to solve the above issues in the elastomer. The elastomer exhibits high toughness (77.3 MJ m-3 ), fracture energy (≈127.2 kJ m-2 ), and good healing efficiency (91 %) at room temperature. The superior performance is ascribed to the inter and intra crosslinking structures of quadruple H-bonding and polyrotaxanes in the dual crosslinking system. Strain-induced crystallization of PEG in polyrotaxanes also contributes to the high fracture energy of the elastomers. Furthermore, based on the dual cross-linked supramolecular elastomer, a highly stretchable and self-healable electrode containing liquid metal is also fabricated, retaining resistance stability (0.16-0.26 Ω) even at the strain of 1600 %.

Versatile self-assembled electrospun micropyramid arrays for high-performance on-skin devices with minimal sensory interference.

On-skin devices that show both high performance and imperceptibility are desired for physiological information detection, individual protection, and bioenergy conversion with minimal sensory interference. Herein, versatile electrospun micropyramid arrays (EMPAs) combined with ultrathin, ultralight, gas-permeable structures are developed through a self-assembly technology based on wet heterostructured electrified jets to endow various on-skin devices with both superior performance and imperceptibility. The designable self-assembly allows structural and material optimization of EMPAs for on-skin devices applied in daytime radiative cooling, pressure sensing, and bioenergy harvesting. A temperature drop of ~4 °C is obtained via an EMPA-based radiative cooling fabric under a solar intensity of 1 kW m-2. Moreover, detection of an ultraweak fingertip pulse for health diagnosis during monitoring of natural finger manipulation over a wide frequency range is realized by an EMPA piezocapacitive-triboelectric hybrid sensor, which has high sensitivity (19 kPa-1), ultralow detection limit (0.05 Pa), and ultrafast response (≤0.8 ms). Additionally, EMPA nanogenerators with high triboelectric and piezoelectric outputs achieve reliable biomechanical energy harvesting. The flexible self-assembly of EMPAs exhibits immense potential in superb individual healthcare and excellent human-machine interaction in an interference-free and comfortable manner.

Bulk Erosion Degradation Mechanism for Poly(1,8-octanediol-co-citrate) Elastomer: An In Vivo and In Vitro Investigation.

As a biodegradable elastomer, poly(1,8-octanediol-co-citrate) (POC) has been widely applied in tissue engineering and implantable electronics. However, the unclear degradation mechanism has posed a great challenge for the better application and development of POC. To reveal the degradation mechanism, here, we present a systematic investigation into in vivo and in vitro degradation behaviors of POC. Initially, critical factors, including chemical structures, hydrophilic and water-absorbency characteristics, and degradation reaction of POC, are investigated. Then, various degradation-induced changes during in vitro degradation of POC-x (POC with different cross-linking densities) are monitored and discussed. The results show that (1) cross-linking densities exponentially drop with degradation time; (2) mass loss and PBS-absorption ratio grow nonlinearly; (3) the morphology on the cross-section changes from flat to rough at a microscopic level; (4) the cubic samples keep swelling until they collapse into fragments from a macro view; and (5) the mechanical properties experience a sharp drop at the beginning of degradation. Finally, the in vivo degradation behaviors of POC-x are investigated, and the results are similar to those in vitro. The comprehensive assessment suggests that the in vitro and in vivo degradation of POC occurs primarily through bulk erosion. Inflammation responses triggered by the degradation of POC-x are comparable to poly(lactic acid), or even less obvious. In addition, the mechanical evaluation of POC in the simulated application environment is first proposed and conducted in this work for a more appropriate application. The degradation mechanism of POC revealed will greatly promote the further development and application of POC-based materials in the biomedical field.

Sliding Cyclodextrin Molecules along Polymer Chains to Enhance the Stretchability of Conductive Composites.

The demand for stretchable electronics with a broader working range is increasing for wide application in wearable sensors and e-skin. However, stretchable conductors based on soft elastomers always exhibit low working range due to the inhomogeneous breakage of the conductive network when stretched. Here, a highly stretchable and self-healable conductor is reported by adopting polyrotaxane and disulfide bonds into the binding layer. The binding layer (PR-SS) builds the bridge between polymer substrates (PU-SS) and silver nanowires (AgNWs). The incorporation of sliding molecules endows the stretchable conductor with a long sensing range (190%) due to the energy dissipation derived from the sliding nature of polyrotaxanes, which is two times higher than the working range (93%) of conductors based on AP-SS without polyrotaxanes. Furthermore, the mechanism of sliding effect for the polyrotaxanes in the elastomers is investigated by SEM for morphological change of AgNWs, in situ small-angle x-ray scattering, as well as stress relaxation experiments. Finally, human-body-related sensing tests and a self-correction system in fitness are designed and demonstrated.

Low Dielectric Poly(imide siloxane) Films Enabled by a Well-Defined Disiloxane-Linked Alkyl Diamine.

This paper presents an efficient pathway to achieve the dielectric constant as low as 2.48 @ 25 °C, 1 MHz for nonporous poly(imide siloxane) films with mechanical and thermal robustness. A symmetric disiloxane-linked alkyl diamine, bis(aminopropyl)tetramethyldisiloxane (BATMS) with a well-defined molecular formula NH2CH2CH2CH2Si(CH3)2OSi(CH3)2CH2CH2CH2NH2, has been used to controllably reduce the dielectric constant of the polymer films by adjusting the loading of BATMS. The thermal stability of all the polymer films remains robust with T 5 and T 10 no less than 458 and 472 °C, respectively, while the glass-transition temperature decreases with increasing incorporation of flexible disiloxane-alkyl segments into a polymer backbone. There exists a consistent regularity between the thermal, optical, and dielectric properties with the loading amount of BATMS in the polymer films, inferring that the disiloxane-alkyl segments are homogeneously distributed in the polymer backbone. Charge-transfer complex inhibition of polymer films by disiloxane segments has been revealed by an enlarged d-spacing in wide-angle X-ray diffraction spectra and a blue shift in film fluorescence emission spectra. The combined low dielectric constant, robust mechanical and thermal stability, and improved hydrophobicity make the series of BATMS-resulting poly(imide siloxane) films promising candidates for sophisticated flexible microelectronic application.