Mechanical reliable,NIR light-induced rapid self-healing hydrogel electrolyte towards flexible zinc-ion hybrid supercapacitors with low-temperature adaptability and long service life

Hydrogel electrolytes hold great potential in flexible zinc ion supercapacitors(ZICs)due to their high conductivity,good safety,and flexibility.However,freezing of electrolytes at low temperature(subzero)leads to drastic reduction in ionic conductivity and mechanical properties that deteriorates the performance of flexible ZICs.Besides,the mechanical fracture during arbitrary deformations significantly prunes out the lifespan of the flexible device.Herein,a Zn^(2+)and Li^(+)co-doped,polypyrrole-dopamine decorated Sb_(2)S_(3)incorporated,and polyvinyl alcohol/poly(N-(2-hydroxyethyl)acrylamide)double-network hydrogel electrolyte is constructed with favorable mechanical reliability,anti-freezing,and self-healing ability.In addition,it delivers ultra-high ionic conductivity of 8.6 and 3.7 S m^(-1)at 20 and−30°C,respectively,and displays excellent mechanical properties to withstand tensile stress of 1.85 MPa with tensile elongation of 760%,together with fracture energy of 5.14 MJ m^(-3).Notably,the fractured hydrogel electrolyte can recover itself after only 90 s of infrared illumination,while regaining 83%of its tensile strain and almost 100%of its ionic conductivity during−30–60°C.Moreover,ZICs coupled with this hydrogel electrolyte not only show a wide voltage window(up to 2 V),but also provide high energy density of 230 Wh kg^(-1)at power density of 500 W kg^(-1)with a capacity retention of 86.7%after 20,000 cycles under 20°C.Furthermore,the ZICs are able to retain excellent capacity even under various mechanical deformation at−30°C.This contribution will open up new insights into design of advanced wearable flexible electronics with environmental adaptability and long-life span.

High performance photodegradation resistant PVA@TiO_(2)/carboxyl-PES self-healing reactive ultrafiltration membrane

The occurrence of ultrafiltration(UF)membrane fouling frequently hampers the sustainable advancement of UF technology.Reactive self-cleaning UF membranes can effectively alleviate the problem of membrane fouling.Nevertheless,the self-cleaning process may accelerate membrane aging.Addressing these concerns,we present an innovative design concept for composite self-healing materials based on self-cleaning UF membranes.To begin,TiO_(2)nanoparticles were incorporated into the polymer molecular structure via molecular design,resulting in the synthesis of TiO_(2)/carboxyl-polyether sulfone(PES)hybrid materials.Subsequently,the nonsolvent-induced phase inversion technique was employed to prepare a novel of UF membrane.Lastly,a polyvinyl alcohol(PVA)hydrogel coating was applied to the hybrid UF membrane surface to create PVA@TiO_(2)/carboxyl-PES self-healing reactive UF membranes.By establishing a covalent bond,the TiO_(2)nanoparticles were effectively and uniformly dispersed within the UF membrane,leading to exceptional self-cleaning properties.Furthermore,the water-absorbing and swelling properties of PVA hydrogel,along with its capacity to form hydrogen bonds with water molecules,resulted in UF membranes with improved hydrophilicity and active self-healing abilities.The results demonstrated that the water contact angle of PVA@5%TiO_(2)/carboxyl-PES UF membrane was 43.1°.Following a 1-h exposure to simulated solar exposure,the water flux recovery ratio increased from 48.16%to 81.03%.Moreover,even after undergoing five cycles of 12-h simulated sunlight exposure,the UF membranes exhibited a consistent retention rate of over 97%,thus fully demonstrating their exceptional self-cleaning,antifouling,and selfhealing capabilities.We anticipate that the self-healing reactive UF membrane system will serve as a pioneering and comprehensive solution for the self-cleaning antifouling challenges encountered in UF membranes while also effectively mitigating the aging effects of reactive UF membranes.

A Self-Healing Optoacoustic Patch with High Damage Threshold and Conversion Efficiency for Biomedical Applications

Compared with traditional piezoelectric ultrasonic devices,optoacoustic devices have unique advantages such as a simple preparation process,anti-electromagnetic interference,and wireless long-distance power supply.However,current optoacoustic devices remain limited due to a low damage threshold and energy conversion efficiency,which seriously hinder their widespread applications.In this study,using a self-healing polydimethylsiloxane(PDMS,Fe-Hpdca-PDMS)and carbon nanotube composite,a flexible optoacoustic patch is developed,which possesses the self-healing capability at room temperature,and can even recover from damage induced by cutting or laser irradiation.Moreover,this patch can generate high-intensity ultrasound(>25 MPa)without the focusing structure.The laser damage threshold is greater than 183.44 mJ cm^(-2),and the optoacoustic energy conversion efficiency reaches a major achievement at 10.66×10^(-3),compared with other carbon-based nanomaterials and PDMS composites.This patch is also been successfully examined in the application of acoustic flow,thrombolysis,and wireless energy harvesting.All findings in this study provides new insight into designing and fabricating of novel ultrasound devices for biomedical applications.

Self-healing Performance of Composite Coatings Prepared by Phosphating and Cerium Nitrate Post-sealing

The phosphated and cerium nitrate post-sealed galvanized steel was firstly scratched to expose zinc layer and then placed in neutral salt spray （NSS） chamber for different durations. The microstructure and compositions of the scratches were investigated using SEM and EDS. The phases of the corrosion products were examined through XRD. The self-healing mechanism of the composite coatings was discussed. The experimental results show that the composite coatings have an excellent corrosion resistance. The corrosion products increase with corrosion time and finally cover the whole scratch. They contain phosphorous, cerium, oxygen, chloride and zinc, and are fine needle and exceedingly compact. The composite coatings are favorable self-healing. During corrosion, the self-healing ions such as Ce3＋, Ce4＋, PO43-, Zn2＋ in the composite coatings were dissolved, migrated, recombined, and covered the exposed zinc, impeding zinc corrosion. The self-healing process of the scratches on the composite coatings can be divided into three stages, about 2 h, 4 h, and 24 h, respectively.

Flexible,thermal processable,self-healing,and fully bio-based starch plastics by constructing dynamic imine network

The serious environmental threat caused by petroleum-based plastics has spurred more researches in developing substitutes from renewable sources.Starch is desirable for fabricating bioplastic due to its abundance and renewable nature.However,limitations such as brittleness,hydrophilicity,and thermal properties restrict its widespread application.To overcome these issues,covalent adaptable network was constructed to fabricate a fully bio-based starch plastic with multiple advantages via Schiff base reactions.This strategy endowed starch plastic with excellent thermal processability,as evidenced by a low glass transition temperature(T_(g)=20.15℃).Through introducing Priamine with long carbon chains,the starch plastic demonstrated superior flexibility(elongation at break=45.2%)and waterproof capability(water contact angle=109.2°).Besides,it possessed a good thermal stability and self-adaptability,as well as solvent resistance and chemical degradability.This work provides a promising method to fabricate fully bio-based plastics as alternative to petroleum-based plastics.

Multifunctional phase change film with high recyclability, adjustable thermal responsiveness, and intrinsic self-healing ability for thermal energy storage

Phase change materials(PCMs) present promising potential for guaranteeing safety in thermal management systems.However,most reported PCMs have a single application in energy storage for thermal management systems,which does not meet the growing demand for multi-functional materials.In this paper,the flexible material and hydrogen-bonding function are innovatively combined to design and prepare a novel multi-functional flexible phase change film(PPL).The 0.2PPL-2 film exhibits solid-solid phase change behavior with energy storage density of 131.8 J/g at the transition temperature of42.1℃,thermal cycling stability(500 cycles),wide-temperature range flexibility(0-60℃) and selfhealing property.Notably,the PPL film can be recycled up to 98.5% by intrinsic remodeling.Moreover,the PPL film can be tailored to the desired colors and configurations and can be cleverly assembled on several thermal management systems at ambient temperature through its flexibility combined with shape-memory properties.More interestingly,the transmittance of PPL will be altered when the ambient temperature changes(60℃),conveying a clear thermal signal.Finally,the thermal energy storage performance of the PPL film is successfully tested by human thermotherapy and electronic device temperature control experiments.The proposed functional integration strategy provides innovative ideas to design PCMs for multifunctionality,and makes significant contributions in green chemistry,highefficiency thermal management,and energy sustainability.

Shear resistance of assembled bentonite interface after confined water saturation and interfacial self-healing capacity

The requisite functions of a bentonite buffer in a deep geological repository depend on the sealing/healing of bentonite interfaces,with particular emphasis on the self-healing(automatic healing upon wetting)of assembled bentonite-bentonite interfaces.This study determined the shear resistance(including the peak shear strength and secant modulus)of densely compacted Gaomiaozi(GMZ)bentonite and its assembled interface after confined water saturation.The effect of bentonite dry density and saturation time on the shear resistance of saturated healed interfaces was elucidated,and the interfacial self-healing capacity was assessed.The results indicate that the shear resistance of the saturated healed interfaces increased with the bentonite dry density but had a non-monotonic correlation with the saturation time.For a given dry density of the bentonite,the saturated healed interface exhibits a lower peak shear strength than the saturated intact bentonite but a higher peak shear strength than the saturated separated interface.The saturated healed and separated interfaces have comparable shear moduli(secant moduli),which are lower than that of the saturated intact bentonite.The saturated healed interfaces display smooth shear failure planes,while the saturated assembled interfaces and intact bentonite exhibit comparable frictional angles.This indicates that interfacial self-healing plays a pivotal role in enhancing interfacial peak shear strength by facilitating microstructural bonding at the assembled interface.Finally,it can be stated that densely compacted GMZ bentonite has a robust interfacial self-healing capacity in terms of shear resistance.These findings contribute to the design of the bentonite buffer and facilitate the evaluation of its safe operation at specified disposal ages.

An intrinsically self-healing and anti-freezing molecular chains induced polyacrylamide-based hydrogel electrolytes for zinc manganese dioxide batteries

The anti-freezing strategy of hydrogels and their self-healing structure are often contradictory,it is vital to break through the molecular structure to design and construct hydrogels with intrinsic anti-freezing/self-healing for meeting the rapid development of flexible and wearable devices in diverse service conditions.Herein,we design a new hydrogel electrolyte(AF/SH-Hydrogel)with intrinsic anti-freezing/self-healing capabilities by introducing ethylene glycol molecules,dynamic chemical bonding(disulfide bond),and supramolecular interaction(multi-hydrogen bond)into the polyacrylamide molecular chain.Thanks to the exceptional freeze resistance(84%capacity retention at-20℃)and intrinsic self-healing capabilities(95%capacity retention after 5 cutting/self-healing cycles),the obtained AF/SH-Hydrogel makes the zinc||manganese dioxide cell an economically feasible battery for the state-of-the-art applications.The Zn||AF/SH-Hydrogel||MnO_(2)device offers a near-theoretical specific capacity of 285 m A h g^(-1)at 0.1 A g^(-1)(Coulombic efficiency≈100%),as well as good self-healing capability and mechanical flexibility in an ice bath.This work provides insight that can be utilized to develop multifunctional hydrogel electrolytes for application in next generation of self-healable and freeze-resistance smart aqueous energy storage devices.

Effect of drying cracks on swelling and self-healing of bentonite-sand blocks used as engineered barriers for radioactive waste disposal

Experiments were conducted to evaluate the healing of drying cracks in air-dried bentonite-sand blocks after hydration and swelling in groundwater,providing justifications to simplify the protection of blocks prior to installation in a high-level radioactive waste repository.Synthetic groundwater was prepared to represent the geochemistry of Beishan groundwater,and was used to hydrate the blocks during the swelling pressure and swelling strain measurements,as Beishan is the most promising site for China's repository.Healing of the surface cracks was recorded by photography,and healing of the internal cracks was visualized by CT images and hydraulic conductivity of air-dried blocks.The results indicate that the maximum swelling pressure and swelling strain are primarily affected by the geochemistry of Beishan groundwater,but not affected by the drying cracks.The maximum swelling pressure and swelling strain of air-dried blocks are comparable to or even higher than the pressure and strain of fresh blocks.The maximum swelling pressure measured in strong(i.e.high ion strength)Beishan groundwater was 44%of the pressure measured in deionized(DI)water,and the maximum swelling strain was reduced to 23%of the strain measured in DI water.Nevertheless,the remained swelling of the blocks hydrated in strong Beishan groundwater was sufficient to heal the surface and internal drying cracks,as demonstrated by the pictures of surface cracks and CT images.The hydraulic conductivity of the air-dried block permeated with strong groundwater was comparable(3.7×higher)to the hydraulic conductivity of the fresh block,indicating the self-healing of drying cracks after hydration and swelling in groundwater.A simplified method of protecting the block with plastic wraps before installation is recommended,since the remained swelling of the block hydrated in Beishan groundwater is sufficient to heal the drying cracks.

An integrated self-healing algorithm for resilient packet ring

Resilient Packet Ring (RPR) is a Media Access Control (MAC) layer protocol that operates over a double counter-rotating ring network topology. RPR is designed to enhance Synchronous Digital Hierarchy(SDH) in order to handle data traffic more efficiently. Since Intelligent Protection Switching(IPS) is one of the key technologies in ring networks, RPR provides two intelligent protection algorithms: steering and wrapping. While wrapping in RPR in essence inherits the automatic protection switching(APS) algorithm of SDH, it also wastes the bandwidth on the wrapping ringlets and may result in severe congestion. Whereas steering in RPR provides high bandwidth utilization, its switching speed is low, because it is indeed a high layer's restoration algorithm. In this paper, integrated self-healing(ISH) algorithm as an effective algorithm for RPR is proposed, which synthesizes the merits of the two algorithms by transporting healing signal and computing routing in MAC layer. At last, the performance of ISH algorithm is analyzed and simulated.

Self-healing mechanism of composite coatings obtained by phosphating and silicate sol post-sealing

Silicate sol post-treatment was applied to form a complete composite coating on the phosphated zinc layer. The chemical compositions of the coatings were investigated using XPS. The coated samples were firstly scratched and then exposed to the neutral salt spray(NSS) chamber for different time. The microstructure and chemical compositions of the scratches were studied using SEM and EDS. And the non-scratched coated samples were compared. The self-healing mechanism of the composite coatings was discussed. The results show that during corrosion, the self-healing ions in composite coatings dissolve, diffuse and transfer to the scratches or the defects, and then recombine with Zn2+ to form insoluble compound, which deposits and covers the exposed zinc. The corrosion products on the scratches contain silicon, phosphorous, oxygen, chloride and zinc, and they are compact, fine, needle and flake, effectively inhibiting the corrosion formation and expansion of the exposed zinc layer. The composite coatings have good self-healing ability.

一种高效的Long-Lived Self-Healing密钥分发机制

对Staddon等人提出的self-healing密钥分发方案作了3个方面的改进:第一,提出了一种更高效的无条件安全的long-lived方案取代基于计算安全的long-lived方案,降低了计算复杂度和通信复杂度;第二,增强了用户恢复合理密钥的能力,使得在某个特殊场景中,用户可以恢复出合理密钥;第三,降低了广播消息的次数和存储在用户端的私人密钥数目.

Microencapsulation of UV-Curable Self-healing Agent for Smart Anticorrosive Coating

UV-curable polyurethane prepolymer and photoinitiator 1173 were facilely encapsulated in a poly（urea-formaldehyde） shell, which was in situ formed by the polymerization of formalde-hyde and urea in an oil-in-water emulsion. The diameters of the microcapsules ranged from 118 μm to 663 μm depending on agitation speed, and were obtained via optical mi-croscopy and scanning electron microscopy analyses. The encapsulation percent and the yield of microcapsules prepared at the agitation speed of 600 r/min can reach 97.52wt% and 65.23wt%, respectively. When the water-borne polyurethane （WPU） coating embedded with the prepared microcapsules were scratched, the healing agent could be released from rup-tured microcapsules and lled the scribed region. The excellent anticorrosion properties of the WPU coating embedded with the prepared microcapsules were con rmed by the results obtained from both electrochemical impedance spectroscopy and Tafel curves.

Self-Healing,Self-Adhesive and Stable Organohydrogel-Based Stretchable Oxygen Sensor with High Performance at Room Temperature

With the advent of the 5G era and the rise of the Internet of Things,various sensors have received unprecedented attention,especially wearable and stretchable sensors in the healthcare field.Here,a stretchable,self-healable,self-adhesive,and room-temperature oxygen sensor with excellent repeatability,a full concentration detection range(0-100%),low theoretical limit of detection(5.7 ppm),high sensitivity(0.2%/ppm),good linearity,excellent temperature,and humidity tolerances is fabricated by using polyacrylamide-chitosan(PAM-CS)double network(DN)organohydrogel as a novel transducing material.The PAM-CS DN organohydrogel is transformed from the PAM-CS composite hydrogel using a facile soaking and solvent replacement strategy.Compared with the pristine hydrogel,the DN organohydrogel displays greatly enhanced mechanical strength,moisture retention,freezing resistance,and sensitivity to oxygen.Notably,applying the tensile strain improves both the sensitivity and response speed of the organohydrogel-based oxygen sensor.Furthermore,the response to the same concentration of oxygen before and after self-healing is basically the same.Importantly,we propose an electrochemical reaction mechanism to explain the positive current shift of the oxygen sensor and corroborate this sensing mechanism through rationally designed experiments.The organohydrogel oxygen sensor is used to monitor human respiration in real-time,verifying the feasibility of its practical application.This work provides ideas for fabricating more stretchable,self-healable,self-adhesive,and high-performance gas sensors using ion-conducting organohydrogels.

Self-Healing Liquid Metal Magnetic Hydrogels for Smart Feedback Sensors and High-Performance Electromagnetic Shielding

Hydrogels exhibit potential applications in smart wearable devices because of their exceptional sensitivity to various external stimuli.However,their applications are limited by challenges in terms of issues in biocompatibility,custom shape,and self-healing.Herein,a conductive,stretchable,adaptable,self-healing,and biocompatible liquid metal GaInSn/Ni-based composite hydrogel is developed by incorporating a magnetic liquid metal into the hydrogel framework through crosslinking polyvinyl alcohol(PVA)with sodium tetraborate.The excellent stretchability and fast self-healing capability of the PVA/liquid metal hydrogel are derived from its abundant hydrogen binding sites and liquid metal fusion.Significantly,owing to the magnetic constituent,the PVA/liquid metal hydrogel can be guided remotely using an external magnetic field to a specific position to repair the broken wires with no need for manual operation.The composite hydrogel also exhibits sensitive deformation responses and can be used as a strain sensor to monitor various body motions.Additionally,the multifunctional hydrogel displays absorption-dominated electromagnetic interference(EMI)shielding properties.The total shielding performance of the composite hydrogel increases to~62.5 dB from~31.8 dB of the pure PVA hydrogel at the thickness of 3.0 mm.The proposed bioinspired multifunctional magnetic hydrogel demonstrates substantial application potential in the field of intelligent wearable devices.

The Prediction of Self-Healing Capacity of Bacteria-Based Concrete Using Machine Learning Approaches

Advances in machine learning(ML)methods are important in industrial engineering and attract great attention in recent years.However,a comprehensive comparative study of the most advanced ML algorithms is lacking.Six integrated ML approaches for the crack repairing capacity of the bacteria-based self-healing concrete are proposed and compared.Six ML algorithms,including the Support Vector Regression(SVR),Decision Tree Regression(DTR),Gradient Boosting Regression(GBR),Artificial Neural Network(ANN),Bayesian Ridge Regression(BRR)and Kernel Ridge Regression(KRR),are adopted for the relationship modeling to predict crack closure percentage(CCP).Particle Swarm Optimization(PSO)is used for the hyper-parameters tuning.The importance of parameters is analyzed.It is demonstrated that integrated ML approaches have great potential to predict the CCP,and PSO is efficient in the hyperparameter tuning.This research provides useful information for the design of the bacteria-based self-healing concrete and can contribute to the design in the rest of industrial engineering.

Self-healing Action of Permeable Crystalline Coating on Pores and Cracks in Cement-based Materials

The self-healing action of a permeable crystalline coating on the po rous mortar was investigated by two times impermeability test. Moreover, the sel f-healing mechanism of cement-based materials with the permeable crystalline c oating was studied by SEM. The results indicate that the permeable crystalline c oating not only seals the pores and cracks in mortar during its curing process, but also heals the permeable pathway caused by first impermeability test or crac ks produced by freeze-thaw cycles. Therefore, cement-based materials can be im proved by the permeable crystalline coating for the self-healing function. SEM images prove that the self-healing function is realized by generating a great q uantity of non-soluble dendritic crystalline within the pores and cracks, which prevents the penetration of water and other liquids.

The study on the mechanical properties of PU/MF double shell self-healing microcapsules

The self-healing microcapsules can be buried in the coating to improve the anticorrosive ability.In this paper,self-healing microcapsules of polyurea(PU)/melamine resin(MF)double shell were prepared by in-situ polymerization and interfacial polymerization with isocyanate as the core material.Scanning electron microscope was used to observe the microcapsule morphology.The structures of microcapsules prepared with different chain extenders were characterized by Fourier transform infrared spectroscopy.The micromanipulation system was used to loading–holding,loading–unloading and loading to rupture individual microcapsules,so as to explore the mechanical properties of microcapsules.The Young’s modulus corresponding to microcapsules was calculated by mathematical model fitting.The self-healing properties of microcapsule coating were characterized by optical microscope.The experimental results showed that the microcapsule shell prepared under optimized conditions had a complete morphology and good mechanical properties.The microcapsule was in the elastic deformation stage under small deformation,and the plastic deformation stage under large deformation.The Young’s modulus range of microcapsules was 9.29–14.51 MPa,and the corresponding Young’s modulus could be prepared by adjusting the process.The surface crack of the coating containing microcapsule could heal itself after48 h in a humid environment.

Distribution of Calcium Carbonate in the Process of Concrete Self-healing

The complete deposition distribution process of calcium carbonate is summarized in three directions of cracks. Distribution of calcium carbonate in the self-healing process of microbial concrete is studied in detail, with the help of a variety of analytical techniques. The results show that carbonate deposits along the x-axis direction of the cracks. The farther from the crack surfaces of concrete matrix in x-axis direction, the more the content of the substrate, the less content of calcium carbonate. Gradual accumulation of calcium carbonate along the y-axis direction is like building a house with bricks. Different repair points are gradually connected, and ultimately the whole of cracks are completely filled. In the z-axis direction, calcium deposits on the surface of fracture direction, when the crack is filled on the surface, because the internal crack hypoxia in the depths of cracks hardly produces calcium carbonate.

Intrinsic Self-Healing Chemistry for Next-Generation Flexible Energy Storage Devices

The booming wearable/portable electronic devices industry has stimulated the progress of supporting flexible energy storage devices.Excellent performance of flexible devices not only requires the component units of each device to maintain the original performance under external forces,but also demands the overall device to be flexible in response to external fields.However,flexible energy storage devices inevitably occur mechanical damages(extrusion,impact,vibration)/electrical damages(overcharge,over-discharge,external short circuit)during longterm complex deformation conditions,causing serious performance degradation and safety risks.Inspired by the healing phenomenon of nature,endowing energy storage devices with self-healing capability has become a promising strategy to effectively improve the durability and functionality of devices.Herein,this review systematically summarizes the latest progress in intrinsic self-healing chemistry for energy storage devices.Firstly,the main intrinsic self-healing mechanism is introduced.Then,the research situation of electrodes,electrolytes,artificial interface layers and integrated devices based on intrinsic self-healing and advanced characterization technology is reviewed.Finally,the current challenges and perspective are provided.We believe this critical review will contribute to the development of intrinsic self-healing chemistry in the flexible energy storage field.