Stable Zinc Anode Facilitated by Regenerated Silk Fibroin-modified Hydrogel Protective Layer.

Inherent dendrite growth and side reactions of zinc anode caused by its unstable interface in aqueous electrolytes severely limit the practical applications of zinc-ion batteries (ZIBs). To overcome these challenges, a protective layer for Zn anode inspired by cytomembrane structure is developed with PVA as framework and silk fibroin gel suspension (SFs) as modifier. This PVA/SFs gel-like layer exerts similar to the solid electrolyte interphase, optimizing the anode-electrolyte interface and Zn2+ solvation structure. Through interface improvement, controlled Zn2+ migration/diffusion, and desolvation, this buffer layer effectively inhibits dendrite growth and side reactions. The additional SFs provide functional improvement and better interaction with PVA by abundant functional groups, achieving a robust and durable Zn anode with high reversibility. Thus, the PVA/SFs@Zn symmetric cell exhibits an ultra-long lifespan of 3150 h compared to bare Zn (182 h) at 1.0 mAh cm-2-1.0 mAh cm-2, and excellent reversibility with an average Coulombic efficiency of 99.04% under a large plating capacity for 800 cycles. Moreover, the PVA/SFs@Zn||PANI/CC full cells maintain over 20 000 cycles with over 80% capacity retention under harsh conditions at 5 and 10 A g-1. This SF-modified protective layer for Zn anode suggests a promising strategy for reliable and high-performance ZIBs.

Synergistic Passivation With Phenylpropylammonium Bromide for Efficient Inverted Perovskite Solar Cells.

Inverted perovskite solar cells (PSCs) are a promising technology for commercialization due to their reliable operation and scalable fabrication. However, in inverted PSCs, depositing a high-quality perovskite layer comparable to those realized in normal structures still presents some challenges. Defects at grain boundaries and interfaces between the active layer and carrier extraction layer seriously hinder the power conversion efficiency (PCE) and stability of these cells. In this work, it is shown that synergistic bulk doping and surface treatment of triple-cation mixed-halide perovskites with phenylpropylammonium bromine (PPABr) can improve the efficiency and stability of inverted PSCs. The PPABr ligand is effective in eliminating halide vacancy defects and uncoordinated Pb2+ ions at both grain boundaries and interfaces. In addition, a 2D Ruddlesden-Popper (2D-RP) perovskite capping layer is formed on the surface of 3D perovskite by using PPABr post-treatment. This 2D-RP perovskite capping layer possesses a concentrated phase distribution ≈n = 2. This capping layer not only reduces interfacial non-radiative recombination loss and improves carrier extraction ability but also promotes stability and efficiency. As a result, the inverted PSCs achieve a champion PCE of over 23%, with an open-circuit voltage as high as 1.15 V and a fill factor of over 83%.

Critical Review of Emerging Pre-metallization Technologies for Rechargeable Metal-Ion Batteries.

Low Coulombic efficiency, low-capacity retention, and short cycle life are the primary challenges faced by various metal-ion batteries due to the loss of corresponding active metal. Practically, these issues can be significantly ameliorated by compensating for the loss of active metals using pre-metallization techniques. Herein, the state-of-the-art development in various pr-emetallization techniques is summarized. First, the origin of pre-metallization is elaborated and the Coulombic efficiency of different battery materials is compared. Second, different pre-metallization strategies, including direct physical contact, chemical strategies, electrochemical method, overmetallized approach, and the use of electrode additives are summarized. Third, the impact of pre-metallization on batteries, along with its role in improving Coulombic efficiency is discussed. Fourth, the various characterization techniques required for mechanistic studies in this field are outlined, from laboratory-level experiments to large scientific device. Finally, the current challenges and future opportunities of pre-metallization technology in improving Coulombic efficiency and cycle stability for various metal-ion batteries are discussed. In particular, the positive influence of pre-metallization reagents is emphasized in the anode-free battery systems. It is envisioned that this review will inspire the development of high-performance energy storage systems via the effective pre-metallization technologies.

Tough and Conductive Nacre-inspired MXene/Epoxy Layered Bulk Nanocomposites.

A long-standing quest in materials science has been the development of tough epoxy resin nanocomposites for use in numerous applications. Inspired by nacre, here we report tough and conductive MXene/epoxy layered bulk nanocomposites. The orientation of MXene lamellar scaffolds is enhanced by annealing treatment. The improved interfacial interactions between MXene lamellar scaffold and epoxy through surface chemical modification resulted in a synergistic effect. Tailoring the interlayer spacing of MXene nanosheets to a critical distance resulted in a fracture toughness about eight times higher than that of pure epoxy, surpassing other epoxy nanocomposites. Our nacre-inspired MXene/epoxy layered bulk nanocomposites also show high electrical conductivity that provides self-monitoring capability for structural integrity and exhibits an excellent electromagnetic interference shielding efficiency. Our proposed strategy provides an avenue for fabricating high-performance epoxy nanocomposites.

Differential Foreign Body Reactions between Branched and Linear Glucomannan Scaffolds.

The extent and patterns of foreign body reaction (FBR) influence the function and feasibility of biomaterials. Polysaccharides, as an important biomaterial category, have received increasing attention in diverse biomaterials design and biomedical applications due to their excellent polymeric and biocompatible characteristics. Their biological effects are usually associated with their monosaccharide composition or functional groups, yet the contribution of their glycan structure is still unknown. Herein, two glucomannans, similar in composition and molecular weight with differences in glycan structure, linear-chain (Konjac glucomannan, KGM), and branched-chain (Bletilla striata polysaccharide, BSP), were adopted to explore the host-biomaterials interaction. After acetyl modification, these polysaccharides were fabricated into electrospun scaffolds to reduce the impacts derived from the physical properties and surface morphology. According to a systematic study of their biological effects on immune cells and host response in a subcutaneous implantation model in vivo, it was revealed that acetyl KGM (acKGM) scaffolds caused a stronger FBR than acetyl BSP materials. Additionally, acKGM could stimulate macrophages to release pro-inflammatory cytokines, suggesting the influence of sugar chain arrangement on FBR and providing clues for the fine regulation of immune response and novel biomaterials design.

A multi-functional zwitterionic hydrogel with unique micro-structure, high elasticity and low modulus.

Owing to their tissue-like softness and low modulus, hydrogels minimize the mechanical mismatch with biological tissues and have received wide attention as biomaterials. However, the development of soft hydrogels is often limited by their brittleness. Here, an ultra-soft and tough hydrogel based on zwitterionic poly(sulfobetaine methacrylate) (PSBMA) was designed and successfully prepared. The obtained PSBMA hydrogel exhibits a unique spike-like micro-structure, low modulus, good stretchability and excellent compressive elasticity, due to the formation of a dual-crosslinking structure. The obtained hydrogel also possesses self-healing properties and electromechanical responses to tensile and compressive deformations. Moreover, the hydrogel has good compatibility attributed to its outstanding anti-protein-adsorption properties.

Conductive silk fibroin hydrogel with semi-interpenetrating network with high toughness and fast self-recovery for strain sensors.

Regenerated silk fibroin (RSF) hydrogels have been extensively studied in the fields of biomedicine and wearable devices in recent years due to their outstanding biocompatibility. However, the pure RSF hydrogels usually exhibited frangibility and low ductility, limiting their application in many aspects severely. Herein, we demonstrate a tough RSF/poly (N, N-dimethylallylamine) hydrogel with semi-interpenetrating network, which possesses good mechanical properties with high stretchability (εb = 900%), tensile strength (σb = 101.7 kPa), toughness (Wf = 516.7 kJ/m3) and tearing fracture energy (T = 407.3 J/m2). Besides, the gels show low residual strain in the cyclic tests and rapid self-recovery (80% toughness recovery within 5 min with the maximum strain of 400%). Moreover, the gels also show high ionic conductivity due to the incorporation of the NaCl and the hydrogel can act as an ideal candidate for strain sensor with high sensitivity (GF = 1.84), admirable linearity, and good durability (1000 cycles with the strain of 100%). When used as a wearable strain sensor for monitoring human movements, it also can detect small and large deformations with high sensitivity. It is expected that this work can provide a new strategy for the fabrication of smart RSF-based hydrogels and expand their application in multiple scenarios.

Surface Passivation Using 2D Perovskites toward Efficient and Stable Perovskite Solar Cells.

3D perovskite solar cells (PSCs) have shown great promise for use in next-generation photovoltaic devices. However, some challenges need to be addressed before their commercial production, such as enormous defects formed on the surface, which result in severe SRH recombination, and inadequate material interplay between the composition, leading to thermal-, moisture-, and light-induced degradation. 2D perovskites, in which the organic layer functions as a protective barrier to block the erosion of moisture or ions, have recently emerged and attracted increasing attention because they exhibit significant robustness. Inspired by this, surface passivation by employing 2D perovskites deposited on the top of 3D counterparts has triggered a new wave of research to simultaneously achieve higher efficiency and stability. Herein, we exploited a vast amount of literature to comprehensively summarize the recent progress on 2D/3D heterostructure PSCs using surface passivation. The review begins with an introduction of the crystal structure, followed by the advantages of the combination of 2D and 3D perovskites. Then, the surface passivation strategies, optoelectronic properties, enhanced stability, and photovoltaic performance of 2D/3D PSCs are systematically discussed. Finally, the perspectives of passivation techniques using 2D perovskites to offer insight into further improved photovoltaic performance in the future are proposed.

Clinical effects of insulin glargine combined with repaglinide in the treatment of type 2 diabetes.

OBJECTIVE: To analyze the clinical effects of insulin glargine combined with repaglinide on the treatment of type 2 diabetes (T2D). METHODS: One hundred and twelve T2D patients were divided into two groups based on the treatment strategy, the control group (N=56) receiving insulin glargine and the experimental group (N=56) receiving insulin glargine combined with repaglinide. Clinical effects were analyzed and compared between the two groups. RESULTS: After treatment, the levels of fasting blood glucose (FBG), 2h-postprandial blood glucose (2h-PBG), and glycosylated hemoglobin of the experimental group were significantly lower than those of the control group (P<0.05). The levels of fasting C-peptide (FCP) and 2h-postprandial C-peptide (2h-PCP) of the experimental group were significantly higher than those of the control group (P<0.05) after treatment. Compared with the control group, the therapeutic efficacy was significantly higher (P<0.05), the time to normal blood glucose was notably shorter (P<0.05), and the insulin dosage was considerably lower in the experimental group (P<0.05). The incidence of adverse effects of the experimental group was significantly lower than that of the control group (P<0.05), and the treatment satisfaction of the experimental group was significantly higher than that of the control group (P<0.05). CONCLUSION: Insulin glargine combined with repaglinide is an effective and safe regimen in clinical practice, which can effectively control the blood glucose level, lower insulin dosage, and reduce adverse effects of T2D.

A flexible quasi-solid-state thermoelectrochemical cell with high stretchability as an energy-autonomous strain sensor.

The design of effective energy systems is crucial for the development of flexible and wearable electronics. Regarding the direct conversion of heat into electricity, thermoelectrochemical cells (TECs) are particularly suitable for low-grade heat harvesting to enable flexible and wearable applications, despite the fact that the electrolyte leakage and complex packaging issues of conventional liquid-based TECs await to be further addressed. Herein, a quasi-solid-state TEC is assembled using the polyacrylamide/acidified-single-walled carbon nanotube (PAAm/a-SWCNT) composite hydrogel, developed via a facile in situ free-radical polymerization route with tin(IV) chloride/tin(II) chloride (Sn4+/Sn2+) as the redox couple. The as-fabricated TEC with a 0.6 wt% a-SWCNT content presents a large thermoelectrochemical Seebeck coefficient of 1.59 ± 0.07 mV K-1 and exhibits excellent stability in thermoelectrochemical performance against large mechanical stretching and deformation. Owing to this superior stretchability, the as-fabricated TEC is further assembled into an energy-autonomous strain sensor, which shows high sensitivity. The strategy of utilizing a quasi-solid-state TEC for energy-autonomous strain sensing unveils the great potential of heat-to-electricity conversion in flexible and wearable electronics.

Construction of Stable Wide-Temperature-Range Proton Exchange Membranes by Incorporating a Carbonized Metal-Organic Frame into Polybenzimidazoles and Polyacrylamide Hydrogels.

Proton exchange membrane fuel cells (PEMFCs) are promising devices for clean power generation in fuel cell electric vehicles applications. The further request of high-efficiency and cost competitive technology make high-temperature proton exchange membranes utilizing phosphoric acid-doped polybenzimidazole be favored because they can work well up to 180 °C without extra humidifier. However, they face quick loss of phosphoric acid below 120 °C and resulting in the limits of commercialization. Herein UiO-66 derived carbon (porous carbon-ZrO2 ), comprising branched poly(4,4'-diphenylether-5,5'-bibenzimidazole) and polyacrylamide hydrogels self-assembly (BHC1-4) membranes for wide-temperature-range operation (80-160 °C) is presented. These two-phase membranes contained the hygroscopicity of polyacrylamide hydrogels improve the low-temperature proton conductivity, relatively enable the membrane to function at 80 °C. An excellent cell performance of BHC2 membrane with high peak power density of 265 and 656 mW cm-2 at both 80 and 160 °C can be achieved. Furthermore, this membrane exhibits high stability of frequency cold start-ups (from room temperature to 80 °C) and long-term cell test at 160 °C. The improvement of cell performance and stability of BHC2 membrane indicate a progress of breaking operated temperature limit in existing PEMFCs systems.

2D Hybrid Halide Perovskites: Structure, Properties, and Applications in Solar Cells.

2D metal-halide perovskites have attracted intense research interest due to superior long-term stability under ambient environments. Compared to their 3D analog, the alternate arrangement of organic and inorganic layers leads to forming a multilayer quantum well (MQW), which endows 2D perovskites with anisotropic optoelectronic properties. In addition, the spacer layer functions as a hydrophobic barrier to effectively prevent 2D perovskite films from ion migration and moisture penetrating, thus realizing outstanding stability. Recently, 2D perovskites have been widely developed with abundant species. The stunning photovoltaic performance with the coexistence of long-term stability and high-power conversion efficiency (PCE) has been realized in 2D perovskite solar cells (PSCs), which paves an avenue for commercialization of PSCs. This review begins with an introduction of crystal structure and crystallization kinetics to illustrate the unique layer characters in 2D perovskites. Then, electron structure, excitons, dielectric confinement, and intrinsic stability properties are discussed in detail. Next, the photovoltaic performance based on recent Ruddlesden-Popper (RP), Dion-Jacobson (DJ), and alternating cations in the interlayer (ACI) phase 2D-PSCs is comprehensively summarized. Finally, the confronting challenges and strategies toward structural design and optoelectronic studies of 2D perovskites are proposed to offer insight into the advanced underlying properties of this family of materials.

Hydrolyzed Hydrogels with Super Stretchability, High Strength, and Fast Self-Recovery for Flexible Sensors.

Polyacrylamide is widely employed in constructing functional hydrogels. However, the volume expansion of this hydrogel in water weakens its mechanical properties and restricts its application. Herein, we report a strategy to convert the swollen and weak polyacrylamide/carboxymethyl chitosan hydrogel into a strong and tough one by hydrolysis in acid solution with an elevated temperature. The obtained hydrolyzed hydrogels possess a high strength, toughness, and tearing fracture energy of 5.9 MPa, 22 MJ/m3 and 7517 J/m2, which are 254, 535 and 186 times higher than those of the original swollen one, respectively. In addition, the gels demonstrate low residual strain and rapid self-recovery abilities. Moreover, the gels have good shape memory behavior controlled by temperature. Furthermore, the gels can be worked as strain sensors with a broad strain window, high sensitivity, excellent linear response, and great durability in monitoring human motions after immersing treatment in a normal saline solution. This work provides a new method for preparing the stretchable and tough polyacrylamide-based hydrogels used in the areas of soft actuators and flexible electronics.

Villi-like poly(acrylic acid) based hydrogel adsorbent with fast and highly efficient methylene blue removing ability.

Organic dye-containing wastewater has become an increasingly serious environmental problem due to the rapid development of the printing and dyeing industry. Hydrogel is a promising adsorbent for organic dyes because of its unique three-dimension network structure and versatile functional groups. Though many efforts have been made in hydrogel adsorbents recently, there is still a critical challenge to fabricate hydrogel adsorbent with high adsorption capacity and high efficiency at the same time. To address this concern, we developed a calcium hydroxide nano-spherulites/poly(acrylic acid -[2-(Methacryloxy)ethyl]trimethyl ammonium chloride) hydrogel adsorbent with novel villi-like structure. The hydrogels were prepared through a simple free radical copolymerization method using calcium hydroxide nano-spherulites as crosslinker. The resultant hydrogel adsorbents showed a maximum adsorption capacity of 2249 mg/g in a 400 mg/L methylene blue solution and a high removal ratio of 98% in 1 h for a 50 mg/L methylene blue solution. In addition, the adsorption behaviors of our hydrogel adsorbents could be well described by pseudo-second-order kinetic model and Langmuir adsorption isotherm model. Furthermore, this kind of hydrogel adsorbent showed selective adsorption behavior for methylene blue. Altogether, the hydrogel adsorbent developed in this work has a high capacity and high efficiency in organic dye removing and promised a great potential in wastewater treatment application.

Printable and Recyclable Conductive Ink Based on a Liquid Metal with Excellent Surface Wettability for Flexible Electronics.

Flexible electronics greatly facilitate human life due to their convenience and comfortable utilization. Liquid metals are an ideal candidate for flexible devices; however, the high surface tension and poor surface wettability restrict their application on diverse substrates. Herein, a printable and recyclable ink composed of poly(vinyl alcohol) and a liquid metal (PVA-LM) was developed to resolve these problems. The materials were designed considering the compatibility between PVA and the liquid metal, and the composite theory was applied to determine the component proportion. The developed composites improved the surface wettability of the liquid metal on diverse substrates, and three-dimensional (3D) printing technology was chosen to maximize the use of this material. Moreover, the PVA-LM ink showed excellent conductivity of about 1.3 × 105 S/m after being turned on, which favored the designing of alarm systems and object locators. The flexible sensors produced with this ink have broad application, high sensitivity, and superstable signal generation even after 200 cycles. When acting as strain sensors, the constructed composites had high sensitivity for monitoring the human movements. Furthermore, liquid metals in printed products can be recycled under alkaline conditions. This study opens a new direction for the next generation of environmentally friendly flexible devices.

A semi-interpenetrating network ionic composite hydrogel with low modulus, fast self-recoverability and high conductivity as flexible sensor.

There is a growing demand for hydrogel-based sensors due to their biomimetic structures and properties, as well as biocompatibility. However, it is still a challenge to fabricate hydrogel sensor with integration of good mechanical properties and high conductivity. Herein, a tough and conductive hydrogel is developed with semi-interpenetrating network formed by incorporating carboxymethyl chitosan and sodium chloride into polyacrylamide network. The hydrogels have high tensile strength, elongation and toughness, but low modulus comparable to human skin. In addition, the hydrogels exhibit fast self-recovery and satisfactory self-healing capabilities. Owing to the existence of sodium chloride, the hydrogel also has high conductivity, good water retention property and anti-freezing ability. When used as a strain sensor, it demonstrates a broad strain window and shows a high sensitivity in monitoring human motions. This work provides a facile method in fabricating multifunctional ionic conductive hydrogel for applications in wearable electronics and soft robotics.

Water Transport Mechanisms of Poly(acrylic acid), Poly(vinyl alcohol), and Poly(ethylene glycol) in C-S-H Nanochannels: A Molecular Dynamics Study.

The transport properties of water molecules in nanochannels are critical to the durability of porous materials. In this article, molecular dynamics simulations are used to study the effects of poly(acrylic acid) (PAA), poly(vinyl alcohol) (PAA), and poly(ethylene glycol) (PEG) on the durability of modified cement-based materials. By establishing ideal composite nanopores, the absorption of water molecules in the channel is simulated. The results show that PEG has the best water-blocking effect under the same simulated conditions, followed by PVA, and PAA is the most unfavorable. This difference in the water-blocking effect can be explained by two factors. On the one hand, hydrophobic alkane groups in these polymers can inhibit water molecule transport. A large number of -COOH and -OH functional groups in PAA and PVA will form a complex H-bond network with the water molecules in the nanopore, dragging the water molecules forward, thereby speeding up the water molecule transmission to a certain extent. However, PEG, which mainly contains low-polar oxygen (C-O-C), has weak hydrogen bonding with water molecules, so the water-blocking effect is more obvious. On the other hand, the van der Waals interaction and the electrostatic interaction mainly derived from Op-Caw-Os can ensure the absorption of the polymer on the C-S-H surface during the transport process. The -COOH in PAA ensures its strongest absorption. But PVA and PEG will morphologically agglomerate during the water absorption, occupying pores and hindering the transport of water molecules.

Experimental Investigation on Graphene Oxide/SrCl2·6H2O Modified CaCl2·6H2O and the Resulting Thermal Performances.

Although the inorganic salt hydrate phase change materials (PCMs) such as CaCl2·6H2O have promising potential for thermal energy storage in building application, the issue of supercooling has restricted their practical application. In this study, graphene oxide (GO) and SrCl2·6H2O as binary nucleation agents were used to modify CaCl2·6H2O and reduce its supercooling degree. Compared with pure CaCl2·6H2O, the incorporation of graphene oxide (GO)/SrCl2·6H2O reduced the supercooling degree to 0.3 °C significantly. In addition, the supercooling degree of modified CaCl2·6H2O after 200 thermal cycles was still much lower than that of non-modified CaCl2·6H2O. From the results of differential scanning calorimetry (DSC), the latent heat value and phase change temperature of the modified CaCl2·6H2O were 207.88 J/g and 27.6 °C, respectively. Aluminum capsules were used to encapsulate the modified PCM and placed inside the composite wallboard. The thermal performances of the composite wallboard with modified PCM were investigated using infrared thermography. Experimental results showed that the average temperature difference between the top and bottom surfaces of modified CaCl2·6H2O/wallboard composite after 1 h heating was kept around 15.8 °C, while it was 4.9 °C for the control wallboard. The above test results proved that the modified CaCl2·6H2O demonstrated good thermal performance and can be used in buildings to maintain thermal comfort.

Mussel-Inspired Adhesive and Tough Hydrogel Based on Nanoclay Confined Dopamine Polymerization.

Adhesive hydrogels are attractive biomaterials for various applications, such as electronic skin, wound dressing, and wearable devices. However, fabricating a hydrogel with both adequate adhesiveness and excellent mechanical properties remains a challenge. Inspired by the adhesion mechanism of mussels, we used a two-step process to develop an adhesive and tough polydopamine-clay-polyacrylamide (PDA-clay-PAM) hydrogel. Dopamine was intercalated into clay nanosheets and limitedly oxidized between the layers, resulting in PDA-intercalated clay nanosheets containing free catechol groups. Acrylamide monomers were then added and in situ polymerized to form the hydrogel. Unlike previous single-use adhesive hydrogels, our hydrogel showed repeatable and durable adhesiveness. It adhered directly on human skin without causing an inflammatory response and was easily removed without causing damage. The adhesiveness of this hydrogel was attributed to the presence of enough free catechol groups in the hydrogel, which were created by controlling the oxidation process of the PDA in the confined nanolayers of clay. This mimicked the adhesion mechanism of the mussels, which maintain a high concentration of catechol groups in the confined nanospace of their byssal plaque. The hydrogel also displayed superior toughness, which resulted from nanoreinforcement by clay and PDA-induced cooperative interactions with the hydrogel networks. Moreover, the hydrogel favored cell attachment and proliferation, owning to the high cell affinity of PDA. Rat full-thickness skin defect experiments demonstrated that the hydrogel was an excellent dressing. This free-standing, adhesive, tough, and biocompatible hydrogel may be more convenient for surgical applications than adhesives that involve in situ gelation and extra agents.

Super stretchable hydrogel achieved by non-aggregated spherulites with diameters <5 nm.

The scope of hydrogel applications can be greatly expanded by the improvement of mechanical properties. However, enhancement of nanocomposite hydrogels (NC gels) has been severely limited because the size of crosslinking nanoparticles is too large, at least in one dimension. Here we report a new strategy to synthesize non-aggregated spherulite nanoparticles, with diameters <5 nm, in aqueous solution, and their enhancement to hydrogel. The stress and stretch ratio at rupture of our NC gel are 430 and 121 KPa with only 40-p.p.m. nanoparticle content. The NC gel containing 200-p.p.m. nanoparticles can revert to 90% of its original size after enduring 100-MPa compressive stress. Our results demonstrate that the suppression of nanoparticle size without aggregation helps to establish a super stretchable and high-toughness hydrogel network at very low inorganic content.