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.

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.

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.

Self-healing Hydrogelsand Underlying Reversible Intermolecular Interactions

Self-healing hydrogels have attracted growing attention over the past decade due to their biomimetic structure,biocompatibility,as well as enhanced lifespan and reliability,thereby have been widely used in various biomedical,electrical and environmental engineering applications.This feature article has reviewed our recent progress in self-healing hydrogels derived from mussel-inspired interactions,multiple hydrogen-bonding functional groups such as 2-ureido-4[1H]-pyrimidinohe(UPy),dynamic covalent bonds(eg,Schiff base reactions and boronic ester bonds).The underlying molecular basics of these interactions,hydrogel preparation principles,and corresponding performances and applications are introduced.The underlying reversible intermolecular interaction mechanisms in these hydrogels were investigated using nanomechanical techniques such as surface forces apparatus(SFA)and atomic force microscopy(AFM),providing fundamental insights into the self-healing mechanisms of the hydrogels.The remaining challenging issues and perspectives in this rapidly developing research area are also discussed.

The design,mechanism and biomedical application of self-healing hydrogels

Hydrogels are promising materials with outstanding characteristics such as tunable and reversible physical/chemical properties,stimuli-responsiveness,biomimetic,and biocompatibility.However,the structural and functional integrity of the hydrogels can be compromised by external mechanical forces or chemical erosion when used,especially in sophisticated in vivo environment.To address this problem,self-healing hydrogels which possess the intrinsic ability of self-repair have been developed to adapt to destructive factors.In this review,we focused on the current advances made in self-healing hydrogels.First,the testing methods for self-healing hydrogels were summarized.Then,we looked into the designing strategies of self-healing hydrogels and illustrated the self-healing mechanism.What＇s more,the biomedical application of self-healing hydrogels in vivo was discussed.

Fluorescent Double Network Hydrogels with Ionic Responsiveness and High Mechanical Properties for Visual Detection

We developed a fluorescent double network hydrogel with ionic responsiveness and high mechanical properties for visual detection.The nanocomposite hydrogel of laponite and polyacrylamide serves as the first network,while the ionic cross-linked hydrogel of terbium ions and sodium alginate serves as the second network.The double-network structure,the introduction of nanoparticles and the reversible ionic crosslinked interactions confer high mechanical properties to the hydrogel.Terbium ions are not only used as the ionic cross-linked points,but also used as green emitters to endow hydrogels with fluorescent properties.On the basis of the “antenna effect” of terbium ions and the ion exchange interaction,the fluorescence of the hydrogels can make selective responses to various ions(such as organic acid radical ions,transition metal ions) in aqueous solutions,which enables a convenient strategy for visual detection toward ions.Consequently,the fluorescent double network hydrogel fabricated in this study is promising for use in the field of visual sensor detection.

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.

Nanozyme‑Engineered Hydrogels for Anti‑Inflammation and Skin Regeneration

Inflammatory skin disorders can cause chronic scarring and functional impairments,posing a significant burden on patients and the healthcare system.Conventional therapies,such as corticosteroids and nonsteroidal anti-inflammatory drugs,are limited in efficacy and associated with adverse effects.Recently,nanozyme(NZ)-based hydrogels have shown great promise in addressing these challenges.NZ-based hydrogels possess unique therapeutic abilities by combining the therapeutic benefits of redox nanomaterials with enzymatic activity and the water-retaining capacity of hydrogels.The multifaceted therapeutic effects of these hydrogels include scavenging reactive oxygen species and other inflammatory mediators modulating immune responses toward a pro-regenerative environment and enhancing regenerative potential by triggering cell migration and differentiation.This review highlights the current state of the art in NZ-engineered hydrogels(NZ@hydrogels)for anti-inflammatory and skin regeneration applications.It also discusses the underlying chemo-mechano-biological mechanisms behind their effectiveness.Additionally,the challenges and future directions in this ground,particularly their clinical translation,are addressed.The insights provided in this review can aid in the design and engineering of novel NZ-based hydrogels,offering new possibilities for targeted and personalized skin-care therapies.

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.

Development of biomedical hydrogels for rheumatoid arthritis treatment

Rheumatoid Arthritis(RA)is an autoimmune disorder that hinders the normal functioning of bones and joints and reduces the quality of human life.Every year,millions of people are diagnosed with RA worldwide,particularly among elderly individuals and women.Therefore,there is a global need to develop new biomaterials,medicines and therapeutic methods for treating RA.This will improve the Healthcare Access and Quality Index and also relieve administrative and financial burdens on healthcare service providers at a global scale.Hydrogels are soft and cross-linked polymeric materials that can store a chunk of fluids,drugs and biomolecules for hydration and therapeutic applications.Hydrogels are biocompatible and exhibit excellent mechanical properties,such as providing elastic cushions to articulating joints by mimicking the natural synovial fluid.Hence,hydrogels create a natural biological environment within the synovial cavity to reduce autoimmune reactions and friction.Hydrogels also lubricate the articulating joint surfaces to prevent degradation of synovial surfaces of bones and cartilage,thus exhibiting high potential for treating RA.This work reviews the progress in injectable and implantable hydrogels,synthesis methods,types of drugs,advantages and challenges.Additionally,it discusses the role of hydrogels in targeted drug delivery,mechanistic behaviour and tribological performance for RA treatment.

Tuning mechanical behaviors of highly entangled hydrogels with the random distribution of mobile entanglements

Highly entangled hydrogels exhibit excellent mechanical properties,including high toughness,high stretchability,and low hysteresis.By considering the evolution of randomly distributed entanglements within the polymer network upon mechanical stretches,we develop a constitutive theory to describe the large stretch behaviors of these hydrogels.In the theory,we utilize a representative volume element(RVE)in the shape of a cube,within which there exists an averaged chain segment along each edge and a mobile entanglement at each corner.By employing an explicit method,we decouple the elasticity of the hydrogels from the sliding motion of their entanglements,and derive the stress-stretch relations for these hydrogels.The present theoretical analysis is in agreement with experiment,and highlights the significant influence of the entanglement distribution within the hydrogels on their elasticity.We also implement the present developed constitutive theory into a commercial finite element software,and the subsequent simulations demonstrate that the exact distribution of entanglements strongly affects the mechanical behaviors of the structures of these hydrogels.Overall,the present theory provides valuable insights into the deformation mechanism of highly entangled hydrogels,and can aid in the design of these hydrogels with enhanced performance.

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.

Ionization Engineering of Hydrogels Enables Highly Efficient Salt‑Impeded Solar Evaporation and Night‑Time Electricity Harvesting

Interfacial solar evaporation holds immense potential for brine desalination with low carbon footprints and high energy utilization.Hydrogels,as a tunable material platform from the molecular level to the macroscopic scale,have been considered the most promising candidate for solar evaporation.However,the simultaneous achievement of high evaporation efficiency and satisfactory tolerance to salt ions in brine remains a challenging scientific bottleneck,restricting the widespread application.Herein,we report ionization engineering,which endows polymer chains of hydrogels with electronegativity for impeding salt ions and activating water molecules,fundamentally overcoming the hydrogel salt-impeded challenge and dramatically expediting water evaporating in brine.The sodium dodecyl benzene sulfonate-modified carbon black is chosen as the solar absorbers.The hydrogel reaches a ground-breaking evaporation rate of 2.9 kg m−2 h−1 in 20 wt%brine with 95.6%efficiency under one sun irradiation,surpassing most of the reported literature.More notably,such a hydrogel-based evaporator enables extracting clean water from oversaturated salt solutions and maintains durability under different high-strength deformation or a 15-day continuous operation.Meantime,on the basis of the cation selectivity induced by the electronegativity,we first propose an all-day system that evaporates during the day and generates salinity-gradient electricity using waste-evaporated brine at night,anticipating pioneer a new opportunity for all-day resource-generating systems in fields of freshwater and electricity.

A self-healing and conductive ionic hydrogel based on polysaccharides for flexible sensors

In this study,we proposed a self-healing conductive hydrogel based on polysaccharides and Li+to serve as flexible sensors.At first,the oxidized sodium alginate(OSA)was obtained through the oxidation reaction of sodium alginate(SA).Then OSA,carboxymethyl chitosan(CMC),and agarose(AGO)were dissolved in LiCl solution,respectively.Finally,the hydrogel was obtained through heating,mixing,and cooling processes.Because of the Schiff base structure and hydrogen bonding,the hydrogel demonstrates good mechanical and self-healing properties.The presence of Li+provides good conductivity for the hydrogel.In addition,we demonstrated the application of the hydrogel as the flexible sensors.It can perceive the process of pressing Morse code with the index finger as a pressure sensor and monitor sliding movement of the thumb as the strain sensor to browse the web with the mobile phone.Thus,the selfhealing conductive hydrogel may have potential applications in flexible wearable sensors.

Biomimetic fibril-like injectable hydrogels for wound management

Soft tissue repair and regeneration present a significant clinical challenge.Soft hydrogels have emerged as a promising solution for promoting stem cell differentiation and facilitating soft tissue formation[1].Various materials,including synthetic polymers like polydimethyl siloxane and natural polymers like proteins,have been be used as hydrogel matrix for hydrogel preparation[2,3].However,the limited biodegradability,inhomogeneous network structure,and inadequate mechanical properties of these hydrogels hinder their long-term application in complex environments in vivo.Inspired by the nanostructure of collagen fibrils,Li et al.developed a strategy for creating injectable nanofibrillar hydrogels by combining self-assembly and chemical crosslinking of nanoparticles[4].Moreover,injectable hydrogels offer advantages as implantable materials,including better defect filling and reduced risk of infection compared to prefabricated hydrogels[5].

Wide temperature range-and damage-tolerant microsupercapacitors from salt-tolerant, anti-freezing and self-healing organohydrogel via dynamic bonds modulation

The advance of microelectronics requires the micropower of microsupercapacitors(MSCs) to possess wide temperature-and damage-tolerance beyond high areal energy density.The properties of electrolyte are crucial for MSCs to meet the above requirements.Here,an organohydrogel electrolyte,featured with high salt tolerance,ultralow freezing point,and strong self-healing ability,is experimentally realized via modulating its inner dynamic bonds.Spectroscopic and theoretical analysis reveal that dimethyl sulfoxide has the ability to reconstruct Li^(+)solvation structure,and interact with free water and polyvinyl alcohol chains via forming hydrogen bonds.The organohydrogel electrolyte is employed to build MSCs,which show a boosted energy density,promising wide temperature range-and damage-tolerant ability.These attractive features make the designed organohydrogel electrolyte have great potential to advance MSCs.

Highly Stretchable and Self-healing Hydrogels Based on Poly(acrylic acid) and Functional POSS

Herein, we present a novel way for the production of self-healing hydrogels with stretch beyond 4200% than their initial length and relatively high tensile strength （0.1-0.25 MPa）. Furthermore, the hydrogel was insensitive to notch. Even for the samples containing V-notches, a stretch of 2300% was demonstrated. The hydrogels were developed by in situ crosslinking of the self-assembled colloidal poly（acrylic acid） （PAA）/functionalized polyhedral oligomeric silsesquioxane （POSS） micelles. This was achieved by the addition of functionalized polyhedral oligomeric silsesquioxane with tertiary amines and hydroxyls （POSS-AH） into the PAA reaction solution. The POSS-AH led to micellar growth, then the dual- crosslinked network was constructed. One type of crosslink was formed by hydrogen-bonding and ionic interactions between PAA chains and POSS-AH, the other type of crosslink was formed by covalent bonds between PAA and bis（N,N＇-methylene- bis-acrylamide）.

Physically Cross-linked Hydrogels with Excellent Self-healing, Moldability, Antibacterial Activities and Adjustable Mechanical Properties

A simple strategy was developed to prepare a tough, self-healing, antibacterial and moldable hydrogel by introducing the natural polyphenolic compound tannic acid(TA) as a cross-linking center for hydrogen bonds. Polyvinyl alcohol(PVA)-TA hydrogel was prepared by physical mixing using PVA as a main component and TA as a cross-linker. There were two types of physical cross linking bonds in the PVA-TA hydrogel network, which were weaker hydrogen bonds between PVA molecular chains and stronger hydrogen bonds between PVA and TA molecules. The mechanical properties and self-healing ability could be adjusted by changing the contents of PVA and TA. The hydrogel possessed not only high mechanical strength(305 kPa tensile strength and 864 kPa compressive strength), moldability and excellent self-healing properties(95% selfhealing efficiency) but also good antibacterial abilities against S. aureus and E. coli. In addition, after soaking the dried hydrogel in 90 ℃ deionized water for 4 h, they could also regain their self-healing ability to a certain extent. The hydrogels have potential applications in the biomedical fields.

Recent advances in calcium alginate hydrogels encapsulating rejuvenator for asphalt self-healing

The inherent self-healing ability of asphalt is insufficient and fails to timely repair the cracks due to the combined effect of temperature variation,air oxidation,ultraviolet exposure and traffic loading.Rejuvenator encapsulation based on self-healing asphalt is a green sustainable preventive maintenance technology for asphalt pavement.During the last decade,rejuvenator encapsulation for asphalt self-healing has been a research hotspot and calcium alginate hydrogels encapsulating rejuvenator is a promising self-healing technology.Hence,this review sheds light on the recent advances of calcium alginate hydrogels encapsulating asphalt rejuvenator including selfhealing capsules and fibers.The synthesis methods of calcium alginate capsules and fibers containing rejuvenator were elaborately introduced,and their surface morphology,interior structure,mechanical strength,thermal stability,rejuvenator content,distribution and survival in asphalt materials were systematically analyzed.Besides,the effect of capsules and fiber on the mechanical property and pavement performance of asphalt concrete were explored.Additionally,a comprehensive review about the effect of calcium alginate capsules and fibers on selfhealing ability of asphalt materials were presented,and the rejuvenator release mechanism and release ratio of them in asphalt mixtures were expounded.In a nutshell,this review aims at highlighting the current research achievements on alginate capsules and fibers containing rejuvenator in asphalt materials,and inspiring enhanced self-healing methods for smart and sustainable maintenance of asphalt pavement.

Self-healing wearable self-powered deep ultraviolet photodetectors based on Ga_(2)O_(3)

Gallium oxide(Ga_(2)O_(3))based flexible heterojunction type deep ultraviolet(UV)photodetectors show excellent solar-blind photoelectric performance,even when not powered,which makes them ideal for use in intelligent wearable devices.How-ever,traditional flexible photodetectors are prone to damage during use due to poor toughness,which reduces the service life of these devices.Self-healing hydrogels have been demonstrated to have the ability to repair damage and their combination with Ga_(2)O_(3) could potentially improve the lifetime of the flexible photodetectors while maintaining their performance.Herein,a novel self-healing and self-powered flexible photodetector has been constructed onto the hydrogel substrate,which exhibits an excellent responsivity of 0.24 mA/W under 254 nm UV light at zero bias due to the built-in electric field originating from the PEDOT:PSS/Ga_(2)O_(3) heterojunction.The self-healing of the Ga_(2)O_(3) based photodetector was enabled by the reversible property of the synthesis of agarose and polyvinyl alcohol double network,which allows the photodetector to recover its original configu-ration and function after damage.After self-healing,the photocurrent of the photodetector decreases from 1.23 to 1.21μA,while the dark current rises from 0.95 to 0.97μA,with a barely unchanged of photoresponse speed.Such a remarkable recov-ery capability and the photodetector’s superior photoelectric performance not only significantly enhance a device lifespan but also present new possibilities to develop wearable and intelligent electronics in the future.