Engineering Sulfur-Containing Polymeric Fire-Retardant Coatings for Fire-Safe Rigid Polyurethane Foam.

With the advantages of lightweight and low thermal conductivity properties, polymeric foams are widely employed as thermal insulation materials for energy-saving buildings but suffer from inherent flammability. Flame-retardant coatings hold great promise for improving the fire safety of these foams without deteriorating the mechanical-physical properties of the foam. In this work, four kinds of sulfur-based flame-retardant copolymers are synthesized via a facile radical copolymerization. The sulfur-containing monomers serve as flame-retardant agents including vinyl sulfonic acid sodium (SPS), ethylene sulfonic acid sodium (VS), and sodium p-styrene sulfonate (VSS). Additionally, 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate are employed to enable a strong interface adhesion with polymeric foams through interfacial H-bonding. By using as-synthesized waterborne flame-retardant polymeric coating with a thickness of 600 µm, the coated polyurethane foam (PUF) can achieve a desired V-0 rating during the vertical burning test with a high limiting oxygen index (LOI) of >31.5 vol%. By comparing these sulfur-containing polymeric fire-retardant coatings, poly(VS-co-HEA) coated PUF demonstrates the best interface adhesion capability and flame-retardant performance, with the lowest peak heat release rate of 166 kW m-2 and the highest LOI of 36.4 vol%. This work provides new avenues for the design and performance optimization of advanced fire-retardant polymeric coatings.

Mitigating Jahn-Teller Effect in Layered Cathode Material Via Interstitial Doping for High-Performance Sodium-Ion Batteries.

Layered transition metal oxides are promising cathode materials for sodium-ion batteries due to their high energy density and appropriate operating potential. However, the poor structural stability is a major drawback to their widespread application. To address this issue, B3+ is successfully introduced into the tetrahedral site of Na0.67 Fe0.5 Mn0.5 O2 , demonstrating the effectiveness of small-radius ion doping in improving electrochemical performance. The obtained Na0.67 Fe0.5 Mn0.5 B0.04 O2 exhibits excellent cycling performance with 88.8% capacity retention after 100 cycles at 1 C and prominent rate performance. The structure-property relationship is constructed subsequently by neutron powder diffraction, in situ X-ray diffraction and X-ray absorption spectroscopy, which reveal that the Jahn-Teller distortion and the consequent P2-P2' phase transformation are effectively mitigated because of the occupancy of B3+ at the interstitial site. Furthermore, it is found that the transition metal layers are stabilized and the transition metal dissolution are suppressed, resulting in excellent cycling performance. Besides, the prominent rate performance is attributed to the enhanced diffusion kinetics associated with the rearrangement of Na+ . This work provides novel insight into the action mechanism of interstitial site doping and demonstrates a universal approach to improve the electrochemical properties of P2-type manganese-based sodium cathode materials.

Molecularly Engineered Lignin-Derived Additives Enable Fire-Retardant, UV-Shielding, and Mechanically Strong Polylactide Biocomposites.

From a perspective of sustainable development and practical applications, there has been a great need for the design of advanced polylactide (PLA) biocomposites that are flame-retardant, ultraviolet (UV)-resistant, and mechanically strong by using biomass-derived additives. Unfortunately, the achievement of a desirable performance portfolio remains unsatisfactory because of improper design strategies. Herein, we report the design of lignin-derived multifunctional bioadditives (TP-g-lignin) with tunable chemical compositions through graft polymerization of a phosphorus-/nitrogen-containing vinyl monomer (TP). Our results show that the incorporation of 5.0 wt % of TP-g-lignin (at a lignin-to-TP ratio of 1:4 by mass) enables PLA to achieve a desirable flame retardancy rating meeting the UL-94 V-0 industrial standard requirements. Meanwhile, the final PLA composite exhibits an exceptional UV-shielding capability. Moreover, with 5.0 wt % of the bio-derived additive, the elastic modulus of PLA is increased by ∼26%, while mechanical strength is fully retained due to engineered favorable interfaces. This work offers an innovative and sustainable strategy for creating bio-based multifunctional additives by using industrial lignin waste and further the application of PLA in the areas of packaging, fabrics, electronics, automobiles, etc.

Stretchable, Ultratough, and Intrinsically Self-Extinguishing Elastomers with Desirable Recyclability.

Advanced elastomers are increasingly used in emerging areas, for example, flexible electronics and devices, and these real-world applications often require elastomers to be stretchable, tough and fire safe. However, to date there are few successes in achieving such a performance portfolio due to their different governing mechanisms. Herein, a stretchable, supertough, and self-extinguishing polyurethane elastomers by introducing dynamic π-π stacking motifs and phosphorus-containing moieties are reported. The resultant elastomer shows a large break strain of ≈2260% and a record-high toughness (ca. 460 MJ m-3 ), which arises from its dynamic microphase-separated microstructure resulting in increased entropic elasticity, and strain-hardening at large strains. The elastomer also exhibits a self-extinguishing ability thanks to the presence of both phosphorus-containing units and π-π stacking interactions. Its promising applications as a reliable yet recyclable substrate for strain sensors are demonstrated. The work will help to expedite next-generation sustainable advanced elastomers for flexible electronics and devices applications.

Dual Modification of P3-Type Layered Cathodes to Achieve High Capacity and Long Cyclability for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) have garnered extensive attentions in recent years as a low-cost alternative to lithium-ion batteries. However, achieving both high capacity and long cyclability in cathode materials remains a challenge for SIB commercialization. P3-type Na0.67Ni0.33Mn0.67O2 cathodes exhibit high capacity and prominent Na+ diffusion kinetics but suffer from serious capacity decay and structural deterioration due to stress accumulation and phase transformations upon cycling. In this work, a dual modification strategy with both morphology control and element doping is applied to modify the structure and optimize the properties of the P3-type Na0.67Ni0.33Mn0.67O2 cathode. The modified Na0.67Ni0.26Cu0.07Mn0.67O2 layered cathode with hollow porous microrod structure exhibits an excellent reversible capacity of 167.5 mAh g-1 at 150 mA g-1 and maintains a capacity above 95 mAh g-1 after 300 cycles at 750 mA g-1. For one thing, the specific morphology shortens the Na+ diffusion pathway and releases stress during cycling, leading to excellent rate performance and high cyclability. For another, Cu doping at the Ni site reduces the Na+ diffusion energy barrier and mitigates unfavorable phase transitions. This work demonstrates that the electrochemical performance of P3-type cathodes can be significantly improved by applying a dual modification strategy, resulting in reduced stress accumulation and optimized Na+ migration behavior for high-performance SIBs.

Synergistic activation of anionic redox via cosubstitution to construct high-capacity layered oxide cathode materials for sodium-ion batteries.

As a potential substitute for lithium-ion battery, sodium-ion batteries (SIBs) have attracted a tremendous amount of attention due to their advantages in terms of cost, safety and sustainability. Nevertheless, further improvement of the energy density of cathode materials in SIBs remains challenging and requires the activation of anion redox reaction (ARR) activity to provide additional capacity. Herein, we report a high-performance Mn-based sodium oxide cathode material, Na0.67Mg0.1Zn0.1Mn0.8O2 (NMZMO), with synergistic activation of ARR by cosubstitution. This material can deliver an ultra-high capacity of âˆ¼233 mAh/g at 0.1 C, which is significantly higher than their single-cation-substituted counterparts and among the best in as-reported MgMn or ZnMn-based cathodes. Various spectroscopic techniques were comprehensively employed and it was demonstrated that the higher capacity of NMZMO originated from the enhanced ARR activity. Neutron pair distribution function and resonant inelastic X-ray scattering experiments revealed that out-of-plane migration of Mg/Zn occurred upon charging and oxygen anions in the form of molecular O2 were trapped in vacancy clusters in the fully-charged-state. In NMZMO, Mg and Zn mutually interacted with each other to migrate toward tetrahedral sites, which provided a prerequisite for further ARR activity enhancement to form more trapped molecular O2. These findings provide unique insight into the ARR mechanism and can guide the development of high-performance cathode materials through ARR enhancement strategies.

Fire Intumescent, High-Temperature Resistant, Mechanically Flexible Graphene Oxide Network for Exceptional Fire Shielding and Ultra-Fast Fire Warning.

Smart fire alarm sensor (FAS) materials with mechanically robust, excellent flame retardancy as well as ultra-sensitive temperature-responsive capability are highly attractive platforms for fire safety application. However, most reported FAS materials can hardly provide sensitive, continuous and reliable alarm signal output due to their undesirable temperature-responsive, flame-resistant and mechanical performances. To overcome these hurdles, herein, we utilize the multi-amino molecule, named HCPA, that can serve as triple-roles including cross-linker, fire retardant and reducing agent for decorating graphene oxide (GO) sheets and obtaining the GO/HCPA hybrid networks. Benefiting from the formation of multi-interactions in hybrid network, the optimized GO/HCPA network exhibits significant increment in mechanical strength, e.g., tensile strength and toughness increase of ~ 2.3 and ~ 5.7 times, respectively, compared to the control one. More importantly, based on P and N doping and promoting thermal reduction effect on GO network, the excellent flame retardancy (withstanding ~ 1200 °C flame attack), ultra-fast fire alarm response time (~ 0.6 s) and ultra-long alarming period (> 600 s) are obtained, representing the best comprehensive performance of GO-based FAS counterparts. Furthermore, based on GO/HCPA network, the fireproof coating is constructed and applied in polymer foam and exhibited exceptional fire shielding performance. This work provides a new idea for designing and fabricating desirable FAS materials and fireproof coatings.

Nanoconfined and in Situ Catalyzed MgH2 Self-Assembled on 3D Ti3C2 MXene Folded Nanosheets with Enhanced Hydrogen Sorption Performances.

MXenes are considered as potential support materials for nanoconfinement of MgH2/Mg to improve the hydrogen storage properties. However, it has never been realized so far due to the stacking and oxidation problems caused by unexpected surface terminations (-OH, -O, etc.) on MXenes. In this study, hexadecyl trimethylammonium bromide was used to build a 3D Ti3C2Tx architecture of folded nanosheets to reduce the stacking risk of flakes, and a bottom-up self-assembly strategy was successfully applied to synthesize ultradispersed MgH2 nanoparticles anchored on the surface of the annealed 3D Ti3C2Tx (Ti-MX). The composite with a 60 wt % loading of MgH2 NPs, 60MgH2@Ti-MX, starts to decompose at 140 °C and is capable of releasing 3.0 wt % H2 at 150 °C within 2.5 h. In addition, a reversible capacity up to 4.0 wt % H2 was still maintained after 60 cycles at 200 °C without obvious loss in kinetics. In situ high-resolution TEM observations of the decomposition process together with other analyses revealed that the nanosize effect caused by the nanoconfinement and the multiphasic interfaces between MgH2(Mg) and Ti-MX, especially the in situ formed catalytic TiH2, were main reasons accounting for the superior hydrogen sorption performances.

Bioinspired, Highly Adhesive, Nanostructured Polymeric Coatings for Superhydrophobic Fire-Extinguishing Thermal Insulation Foam.

Lightweight polymeric foam is highly attractive as thermal insulation materials for energy-saving buildings but is plagued by its inherent flammability. Fire-retardant coatings are suggested as an effective means to solve this problem. However, most of the existing fire-retardant coatings suffer from poor interfacial adhesion to polymeric foam during use. In nature, snails and tree frogs exhibit strong adhesion to a variety of surfaces by interfacial hydrogen-bonding and mechanical interlocking, respectively. Inspired by their adhesion mechanisms, we herein rationally design fire-retardant polymeric coatings with phase-separated micro/nanostructures via a facile radical copolymerization of hydroxyethyl acrylate (HEA) and sodium vinylsulfonate (VS). The resultant waterborne poly(VS-co-HEA) copolymers exhibit strong interfacial adhesion to rigid polyurethane (PU) foam and other substrates, better than most of the current adhesives because of the combination of interfacial hydrogen-bonding and mechanical interlocking. Besides a superhydrophobic feature, the poly(VS-co-HEA)-coated PU foam can self-extinguish a flame, exhibiting a desired V-0 rating during vertical burning and low heat and smoke release due to its high charring capability, which is superior to its previous counterparts. Moreover, the foam thermal insulation is well-preserved and agrees well with theoretical calculations. This work offers a facile biomimetic strategy for creating advanced adhesive fire-retardant polymeric coatings for many flammable substrates.

Dynamic Nanoconfinement Enabled Highly Stretchable and Supratough Polymeric Materials with Desirable Healability and Biocompatibility.

Lightweight polymeric materials are highly attractive platforms for many potential industrial applications in aerospace, soft robots, and biological engineering fields. For these real-world applications, it is vital for them to exhibit a desirable combination of great toughness, large ductility, and high strength together with desired healability and biocompatibility. However, existing material design strategies usually fail to achieve such a performance portfolio owing to their different and even mutually exclusive governing mechanisms. To overcome these hurdles, herein, for the first time a dynamic hydrogen-bonded nanoconfinement concept is proposed, and the design of highly stretchable and supratough biocompatible poly(vinyl alcohol) (PVA) with well-dispersed dynamic nanoconfinement phases induced by hydrogen-bond (H-bond) crosslinking is demonstrated. Because of H-bond crosslinking and dynamic nanoconfinement, the as-prepared PVA nanocomposite film exhibits a world-record toughness of 425 ± 31 MJ m-3 in combination with a tensile strength of 98 MPa and a large break strain of 550%, representing the best of its kind and even outperforming most natural and artificial materials. In addition, the final polymer exhibits a good self-healing ability and biocompatibility. This work affords new opportunities for creating mechanically robust, healable, and biocompatible polymeric materials, which hold great promise for applications, such as soft robots and artificial ligaments.

A Durable, Flexible, Large-Area, Flame-Retardant, Early Fire Warning Sensor with Built-In Patterned Electrodes.

Fire has been giving rise to enormous loss of life and property worldwide annually. Early fire warning represents an active and effective means to avoid potential fire hazards before huge losses occur. Despite encouraging advances in early fire warning systems, to date there remains an urgent lack of the design of a durable, flexible, and universal early fire warning sensor for large-area practical applications. Herein, facile fabrication of a durable, flexible, large-scale early fire-warning sensor is demonstrated through constructing a hierarchical flame retardant nanocoating, composed of graphene oxide, poly(dimethylaminoethyl methacrylate), and hexagonal boron nitride, on cotton fabric in combination with the parallelly patterned conductive ink as built-in electrodes. As-designed large-scale sensor (>33 cm and extendable) exhibits a short alarming time of <3 s in response to external abnormal high temperature, heat, or fire. In addition to high washability, flexibility, resistance to abrasion and wear, this hierarchical nanocoating can self-extinguish, thus enabling the sensor to continue warning during fire. This work offers an inventive concept to develop a universal and large-scale very early fire-monitoring platform, which opens up new opportunities for their practical applications in effectively reducing fire-related casualties and economic losses.

Using a Self-Assembled Two-Dimensional MXene-Based Catalyst (2D-Ni@Ti3C2) to Enhance Hydrogen Storage Properties of MgH2.

In this work, we report the remarkable catalytic effects of a novel Ti3C2 MXene-based catalyst (Ni@Ti-MX), which was prepared via self-assembling of Ni nanoparticles onto the surface of exfoliated Ti3C2 nanosheets. The resultant Ni@Ti-MX catalyst, characterized by ultradispersed Ni nanoparticles being anchored on the monolayer Ti3C2 flakes, was introduced into MgH2 through ball milling. In situ transmission electron microscopy (TEM) analysis revealed that a synergetic catalytic effect of multiphase components (Mg2Ni, TiO2, metallic Ti, etc.) derived in the MgH2 + Ni@Ti-MX composite exhibits remarkable improvements in the hydrogen sorption kinetics of MgH2. In particular, the MgH2 + Ni@Ti-MX composite can absorb 5.4 wt % H2 in 25 s at 125 °C and release 5.2 wt % H2 in 15 min at 250 °C. Interestingly, it can uptake 4 wt % H2 in 5 h even at room temperature. Furthermore, the dehydrogenation peak temperature of the MgH2 + Ni@Ti-MX composite is about 221 °C, which is 50 and 122 °C lower than that of MgH2 + Ti-MX and MgH2, respectively. The excellent hydrogen sorption properties of the MgH2 + Ni@Ti-MX composite are primarily attributed to the peculiar core-shell nanostructured MgH2@Mg2NiH4 hybrid materials and the interfacial coupling effects from different catalyst-matrix interfaces. The results obtained in this study demonstrate that using self-assembling of transition-metal elements on two-dimensional (2D) materials as a catalyst is a promising approach to enhance the hydrogen storage properties of MgH2.