Self‐Healing Materials for Energy‐Storage Devices

The booming development of electronics, electric vehicles, and grid storage stations has led to a high demand for advanced energy‐storage devices (ESDs) and accompanied attention to their reliability under various circumstances. Self‐healing is the ability of an organism to repair damage and restore function through its own internal vitality. Inspired by this, brilliant designs have emerged in recent years using self‐healing materials to significantly improve the lifespan, durability, and safety of ESDs. Extrinsic and intrinsic self‐healing materials and their working principles are first introduced. Then, the application of self‐healing materials in ESDs according to their self‐healing chemistry, including hydrogen bonds, electrostatic interactions, and borate ester bonds, are described in detail. Based on these, critical challenges and important future directions of self‐healing ESDs are discussed.     

Developments and Challenges in Self‐Healing Antifouling Materials

Self‐healing antifouling materials have gained rapidly increasing interest over the past decade and have been studied and used in a rapidly increasing range of applications. Recent developments and challenges in self‐healing antifouling materials are summarized in four sections: first, the different mechanisms for both antifouling and self‐healing are briefly discussed. Second, three main categories of self‐healing antifouling materials based on surface replenishing and dynamic covalent and noncovalent interactions are discussed, with a focus on the preparation, characterization, and central characteristics of different self‐healing antifouling materials. Third, different types of potential applications of self‐healing antifouling materials are summarized, such as injectable hydrogels and oil/water separations. Finally, a summary of future development of the field is provided, and a number of critical limitations that are still outstanding are highlighted.     

Self‐Healing Silk Fibroin‐Based Hydrogel for Bone Regeneration: Dynamic Metal‐Ligand Self‐Assembly Approach

Despite advances in the development of silk fibroin (SF)‐based hydrogels, current methods for SF gelation show significant limitations such as lack of reversible crosslinking, use of nonphysiological conditions, and difficulties in controlling gelation time. In the present study, a strategy based on dynamic metal‐ligand coordination chemistry is developed to assemble SF‐based hydrogel under physiological conditions between SF microfibers (mSF) and a polysaccharide binder. The presented SF‐based hydrogel exhibits shear‐thinning and autonomous self‐healing properties, thereby enabling the filling of irregularly shaped tissue defects without gel fragmentation. A biomineralization approach is used to generate calcium phosphate‐coated mSF, which is chelated by bisphosphonate ligands of the binder to form reversible crosslinkages. Robust dually crosslinked (DC) hydrogel is obtained through photopolymerization of acrylamide groups of the binder. DC SF‐based hydrogel supports stem cell proliferation in vitro and accelerates bone regeneration in cranial critical size defects without any additional morphogenes delivered. The developed self‐healing and photopolymerizable SF‐based hydrogel possesses significant potential for bone regeneration application with the advantages of injectability and fit‐to‐shape molding.     

Acylhydrazones as Reversible Covalent Crosslinkers for Self‐Healing Polymers

The utilization of dynamic covalent and noncovalent bonds in polymeric materials offers the possibility to regenerate mechanical damage, inflicted on the material, and is therefore of great interest in the field of self‐healing materials. For the design of a new class of self‐healing materials, methacrylate containing copolymers with acylhydrazones as reversible covalent crosslinkers are utilized. The self‐healing polymer networks are obtained by a bulk polymerization of an acylhydrazone crosslinker and commercially available methacrylates as comonomers to fine‐tune the T_g of the systems. The influence of the amount of acylhydrazone crosslinker and the self‐healing behavior of the polymers is studied in detail. Furthermore, the basic healing mechanism and the corresponding mechanical properties are analyzed.     

Self‐Healing and Stretchable 3D‐Printed Organic Thermoelectrics

With the advent of flexible and wearable electronics and sensors, there is an urgent need to develop energy‐harvesting solutions that are compatible with such wearables. However, many of the proposed energy‐harvesting solutions lack the necessary mechanical properties, which make them susceptible to damage by repetitive and continuous mechanical stresses, leading to serious degradation in device performance. Developing new energy materials that possess high deformability and self‐healability is essential to realize self‐powered devices. Herein, a thermoelectric ternary composite is demonstrated that possesses both self‐healing and stretchable properties produced via 3D‐printing method. The ternary composite films provide stable thermoelectric performance during viscoelastic deformation, up to 35% tensile strain. Importantly, after being completely severed by cutting, the composite films autonomously recover their thermoelectric properties with a rapid response time of around one second. Using this self‐healable and solution‐processable composite, 3D‐printed thermoelectric generators are fabricated, which retain above 85% of their initial power output, even after repetitive cutting and self‐healing. This approach represents a significant step in achieving damage‐free and truly wearable 3D‐printed organic thermoelectrics.     

Self‐Replenishing Dual Structured Superhydrophobic Coatings Prepared by Drop‐Casting of an All‐In‐One Dispersion

Robust dual structured superhydrophobic coatings which replenish spontaneously their surface chemical composition on new multi‐scale structured surfaces, recreated upon damage, are described. The surface repair occurs at room temperature, via intrinsic elements of the coatings, all covalently bonded. These coatings can be prepared from all‐in‐one dispersions by a simple drop‐cast method, with different thicknesses and on various substrates. The critical factors to optimize the self‐replenishment are described and three main design principles are postulated. The superhydrofobicity of the coatings is maintained even after 500 abrasion cycles. The principles reported can be extended towards self‐healing other surface‐dependent functionalities, that is, anti‐bacteria, anti‐fouling, or drag‐reduction, which will maintain high performance levels all through their life‐cycle with low cost and energy demand for maintenance and surface repair.     

Electrical and Mechanical Self‐Healing in High‐Performance Dielectric Elastomer Actuator Materials

Dielectric elastomers are of interest for actuator applications due to their large actuation strain, high bandwidth, high energy density, and their flexible nature. If future dielectric elastomers are to be used reliably in applications that include soft robotics, medical devices, artificial muscles, and electronic skins, there is a need to design devices that are tolerant to electrical and mechanical damage. In this paper, the first report of self‐healing of both electrical breakdown and mechanical damage in dielectric actuators using a thermoplastic methyl thioglycolate–modified styrene–butadiene–styrene (MGSBS) elastomer is provided. The self‐healing functions are examined from the material to device level by detailed examination of the healing process, and characterization of electrical properties and actuator response before and after healing. It is demonstrated that after dielectric breakdown, the initial dielectric strength can be recovered by up to 67%, and after mechanical damage, a 39% recovery can be achieved with no degradation of the strain–voltage response of the actuators. The elastomer can also heal a combination of mechanical and electrical failures. This work provides a route to create robust and damage tolerant dielectric elastomers for soft robotic and other applications related to actuator and energy‐harvesting systems.     

Accelerated Self‐Healing Via Ternary Interpenetrating Microvascular Networks

Self‐healing materials with dual interpenetrating microvascular networks enable two‐part healing chemistries and repeated healing of damage in a localized region. 1 However, due to slow healing kinetics, multiple days are required between damage events to recover mechanical performance under ambient conditions. By directly writing a third interdigitated microvascular network within these epoxy coating/substrate architectures to enable in situ thermal regulation, the characteristic healing time is reduced by an order of magnitude. Specifically, this third network provides a conduit for circulating a temperature‐controlled fluid that rapidly heats the locally damaged region leading to a sharp reduction in the time required for mechanical property restoration.     

Novel Biocompatible Polysaccharide‐Based Self‐Healing Hydrogel

A novel biocompatible polysaccharide‐based self‐healing hydrogel, CEC‐l‐OSA‐l‐ADH hydrogel (“l” means “linked‐by”), is developed by exploiting the dynamic reaction of N‐carboxyethyl chitosan (CEC) and adipic acid dihydrazide (ADH) with oxidized sodium alginate (OSA). The self‐healing ability, as demonstrated by rheological recovery, macroscopic observation, and beam‐shaped strain compression measurement, is attributed to the coexistence of dynamic imine and acylhydrazone bonds in the hydrogel networks. The CEC‐l‐OSA‐l‐ADH hydrogel shows excellent self‐healing ability under physiological conditions with a high healing efficiency (up to 95%) without need for any external stimuli. In addition, the CEC‐l‐OSA‐l‐ADH hydrogel exhibits good cytocompatibility and cell release as demonstrated by three‐dimensional cell encapsulation. With these superior properties, the developed hydrogel holds great potential for applications in various biomedical fields, e.g., as cell or drug delivery carriers.     

Autonomous Self‐Healing of Epoxy Thermosets with Thiol‐Isocyanate Chemistry

Thiol‐isocyanate chemistry, combined with a dual capsule strategy, is used for the development of extrinsic self‐healing epoxy materials. It is shown that the amine groups present in the matrix both serve as a catalyst for the addition reaction between a thiol and an isocyanate and as a way to covalently link the healed network structure to the surrounding resin. The tapered double cantilever beam (TDCB) geometry is used for evaluating the recovery of the fracture toughness at room temperature after different healing times. Using manual injection of the healing agents into the crack, a healing efficiency up to 130% is obtained for the EPIKOTE 828/DETA epoxy material. On the other hand, when two types of microcapsules, one containing a tetrathiol reagent and the other a low toxic isocyanate reagent, are incorporated into this epoxy thermoset (20 wt%), a recovery of more than 50% is reached. The influence of parameters such as the amount and core content of the microcapsules on the healing efficiency is investigated. Furthermore, the thiol‐isocyanate chemistry is also tested for an industrial cold‐curing epoxy resin (RIM 135/RIMH 137).     

Autonomic Self‐Healing of PEDOT:PSS Achieved Via Polyethylene Glycol Addition

Self‐healing electronic materials are of primary interest for bioelectronics and sustainable electronics. In this work, autonomic self‐healing of films obtained from mixtures of the conducting polymer poly(3,4‐ethylenedioxythiophene) doped with polystyrene sulfonate (PEDOT:PSS) and polyethylene glycol (PEG) is reported. The presence of PEG in PEDOT:PSS films decreases the elastic modulus and increases the elongation at break, thus leading to a softer material with enhanced self‐healing characteristics. In situ imaging of the cutting/healing process shows that the healing mechanism is likely due to flowing back of the material to the damaged area right after the cutting.     

Delivery of Two‐Part Self‐Healing Chemistry via Microvascular Networks

Multiple healing cycles of a single crack in a brittle polymer coating are achieved by microvascular delivery of a two‐part, epoxy‐based self‐healing chemistry. Epoxy resin and amine‐based curing agents are transported to the crack plane through two sets of independent vascular networks embedded within a ductile polymer substrate beneath the coating. The two reactive components remain isolated and stable in the vascular networks until crack formation occurs in the coating under a mechanical load. Both healing components are wicked by capillary forces into the crack plane, where they react and effectively bond the crack faces closed. Healing efficiencies of over 60% are achieved for up to 16 intermittent healing cycles of a single crack, which represents a significant improvement over systems in which a single monomeric healing agent is delivered.     

Self‐Healing,Flexible, and Tailorable Triboelectric Nanogenerators for Self‐Powered Sensors based on Thermal Effect of Infrared Radiation

Self‐healing triboelectric nanogenerators (TENGs) with flexibility, robustness, and conformability are highly desirable for promising flexible and wearable devices, which can serve as a durable, stable, and renewable power supply, as well as a self‐powered sensor. Herein, an entirely self‐healing, flexible, and tailorable TENG is designed as a wearable sensor to monitor human motion, with infrared radiation from skin to promote self‐healing after being broken based on thermal effect of infrared radiation. Human skin is a natural infrared radiation emitter, providing favorable conditions for the device to function efficiently. The reversible imine bonds and quadruple hydrogen bonding (UPy) moieties are introduced into polymer networks to construct self‐healable electrification layer. UPy‐functionalized multiwalled carbon nanotubes are further incorporated into healable polymer to obtain conductive nanocomposite. Driven by the dynamic bonds, the designed and synthesized materials show excellent intrinsic self‐healing and shape‐tailorable features. Moreover, there is a robust interface bonding in the TENG devices due to the similar healable networks between electrification layer and electrode. The output electric performances of the self‐healable TENG devices can almost restore their original state when the damage of the devices occurs. This work presents a novel strategy for flexible devices, contributing to future sustainable energy and wearable electronics.     

Embedded Shape‐Memory Alloy Wires for Improved Performance of Self‐Healing Polymers

We report the first measurements of self‐healing polymers with embedded shape‐memory alloy (SMA) wires. The addition of SMA wires shows improvements of healed peak fracture loads by up to a factor of 1.6, approaching the performance of the virgin material. Moreover, the repairs can be achieved with reduced amounts of healing agent. The improvements in performance are due to two main effects: (i) crack closure, which reduces the total crack volume and increases the crack fill factor for a given amount of healing agent and (ii) heating of the healing agent during polymerization, which increases the degree of cure of the polymerized healing agent.     

Fabrication of All‐Water‐Based Self‐Repairing Superhydrophobic Coatings Based on UV‐Responsive Microcapsules

Superhydrophobic coatings that are also self‐healing have drawn much attention in recent years for improved durability in practical applications. Typically, the release of the self‐healing agents is triggered by temperature and moisture change. In this study, UV‐responsive microcapsules are successfully synthesized by Pickering emulsion polymerization using titania (TiO₂) and silica (SiO₂) nanoparticles as the Pickering agents to fabricate all‐water‐based self‐repairing, superhydrophobic coatings. These coatings are environmentally friendly and can be readily coated on various substrates. Compared to conventional superhydrophobic coatings, these coatings can regenerate superhydrophobicity and self‐cleaning ability under UV light, mimicking the outdoor environment, after they are mechanically damaged or contaminated with organics. They can maintain the superhydrophobicity after multiple cycles of accelerated weathering tests.     

Ultrauniform Embedded Liquid Metal in Sulfur Polymers for Recyclable,Conductive, and Self‐Healable Materials

Liquid metals (LMs) are receiving growing interest in modern technologies for their various advantages. This work reports using elemental sulfur to achieve nanodispersed liquid metals in bulk polymers for multifunctional LM‐based materials. Ring‐opening polymerization and inverse vulcanization of elemental sulfur provide many polysulfide loops and thiol groups as effective binding ligands that enable extraordinarily uniform dispersion of liquid metals (≈1 µm) in bulk matrix and improve the mechanical performance of the materials. Interestingly, the liquid‐metal‐embedded sulfur polymer (LMESP) materials exhibit excellent thermal‐/solvent‐processability and recyclability. The uniform dispersion leads to phenomenal electrical conductivity of the LMESP at a low volume percentage of LM (30 vol%), overcoming the issue of nonconductivity typically seen in insulated LM–polymer blends. Additionally, the LMESP shows resistive sensitivity toward external pressure. Furthermore, the LMESP materials exhibit an excellent self‐healing ability under mild conditions via the dynamic bonds between polysulfide loops/thiol groups and liquid metals. This work clearly offers a new platform to design liquid metals and can push them for broad applications.     

Self‐Healing Materials via Reversible Crosslinking of Poly(ethylene oxide)‐Block‐Poly(furfuryl glycidyl ether) (PEO‐b‐PFGE) Block Copolymer Films

The application of well‐defined poly(furfuryl glycidyl ether) (PFGE) homopolymers and poly(ethylene oxide)‐b‐poly(furfuryl glycidyl ether) (PEO‐b‐PFGE) block copolymers synthesized by living anionic polymerization as self‐healing materials is demonstrated. This is achieved by thermo‐reversible network formation via (retro) Diels‐Alder chemistry between the furan groups in the side‐chain of the PFGE segments and a bifunctional maleimide crosslinker within drop‐cast polymer films. The process is studied in detail by differential scanning calorimetry (DSC), depth‐sensing indentation, and profilometry. It is shown that such materials are capable of healing complex scratch patterns, also multiple times. Furthermore, microphase separation within PEO‐b‐PFGE block copolymer films is indicated by small angle X‐ray scattering (lamellar morphology with a domain spacing of approximately 19 nm), differential scanning calorimetry, and contact angle measurements.