Highly Stretchable and Tough Hydrogels below Water Freezing Temperature

Hydrogels consist of hydrophilic polymer networks dispersed in water. Many applications of hydrogels rely on their unique combination of solid‐like mechanical behavior and water‐like transport properties. If the temperature is lowered below 0 °C, however, hydrogels freeze and become rigid, brittle, and non‐conductive. Here, a general class of hydrogels that do not freeze at temperatures far below 0 °C, while retaining high stretchability and fracture toughness, is demonstrated. These hydrogels are synthesized by adding a suitable amount of an ionic compound to the hydrogel. The present study focuses on tough polyacrylamide‐alginate double network hydrogels equilibrated with aqueous solutions of calcium chloride. The resulting hydrogels can be cooled to temperatures as low as ?57 °C without freezing. In this temperature range, the hydrogels can still be stretched more than four times their initial length and have a fracture toughness of 5000 J m^?2. It is anticipated that this new class of hydrogels will prove useful in developing new applications operating under a broad range of environmental and atmospheric conditions.     

Muscle‐Inspired Highly Anisotropic,Strong, Ion‐Conductive Hydrogels

Biological tissues generally exhibit excellent anisotropic mechanical properties owing to their well‐developed microstructures. Inspired by the aligned structure in muscles, a highly anisotropic, strong, and conductive wood hydrogel is developed by fully utilizing the high–tensile strength of natural wood, and the flexibility and high‐water content of hydrogels. The wood hydrogel exhibits a high–tensile strength of 36 MPa along the longitudinal direction due to the strong bonding and cross‐linking between the aligned cellulose nanofibers (CNFs) in wood and the polyacrylamide (PAM) polymer. The wood hydrogel is 5 times and 500 times stronger than the bacterial cellulose hydrogels (7.2 MPa) and the unmodified PAM hydrogel (0.072 MPa), respectively, representing one of the strongest hydrogels ever reported. Due to the negatively charged aligned CNF, the wood hydrogel is also an excellent nanofluidic conduit with an ionic conductivity of up to 5 × 10^?4 S cm^–1 at low concentrations for highly selective ion transport, akin to biological muscle tissue. The work offers a promising strategy to fabricate a wide variety of strong, anisotropic, flexible, and ionically conductive wood‐based hydrogels for potential biomaterials and nanofluidic applications.     

Printable Superelastic Conductors with Extreme Stretchability and Robust Cycling Endurance Enabled by Liquid‐Metal Particles

Stretchable conductors are vital and indispensable components in soft electronic systems. The development for stretchable conductors has been highly motivated with different approaches established to address the dilemma in the conductivity and stretchability trade‐offs to some extent. Here, a new strategy to achieve superelastic conductors with high conductivity and stable electrical performance under stretching is reported. It is demonstrated that by electrically anchoring conductive fillers with eutectic gallium indium particles (EGaInPs), significant improvement in stretchability and durability can be achieved in stretchable conductors. Different from the strategy of modulating the chemical interactions between the conductive fillers and host polymers, the EGaInPs provide dynamic and robust electrical anchors between the conductive fillers. A superelastic conductor which can achieve a high stretchability with 1000% strain at initial conductivity of 8331 S cm^?1 and excellent cycling durability with about eight times resistance change (compared to the initial resistance at 0% strain before stretching) after reversibly stretching to 800% strain for 10 000 times is demonstrated. Applications of the superelastic conductor in an interactive soft touch device and a stretchable light‐emitting system are also demonstrated, featuring its promising applications in soft robotics or soft and interactive human–machine interfaces.     

Highly Stretchable Metallic Nanowire Networks Reinforced by the Underlying Randomly Distributed Elastic Polymer Nanofibers via Interfacial Adhesion Improvement

On‐skin electronics require conductive, porous, and stretchable materials for a stable operation with minimal invasiveness to the human body. However, porous elastic conductors that simultaneously achieve high conductivity, good stretchability, and durability are rare owing to the lack of proper design for good adhesion between porous elastic polymer and conductive metallic networks. Here, a simple fabrication approach for porous nanomesh‐type elastic conductors is shown by designing a layer‐by‐layer structure of nanofibers/nanowires (NFs/NWs) via interfacial hydrogen bonding. The as‐prepared conductors, consisting of Ag NWs and polyurethane (PU) NFs, simultaneously achieve high conductivity (9190 S cm^?1), high stretchability (310%), and good durability (82% resistance increase after 1000 cycles of deformation at 70% tensile strain). The direct contact between the Ag NWs enables the high conductivity. The synergistic effect of the layer‐by‐layer structure and good adhesion between the Ag NWs and the PU NFs enables good mechanical properties. Furthermore, without any adhesive gel/tape, the conductors can be utilized as breathable strain sensors for precise joint motion monitoring, and as breathable sensing electrodes for continuous electrophysiological signal recording.     

Adhesive Hemostatic Conducting Injectable Composite Hydrogels with Sustained Drug Release and Photothermal Antibacterial Activity to Promote Full‐Thickness Skin Regeneration During Wound Healing

Developing injectable nanocomposite conductive hydrogel dressings with multifunctions including adhesiveness, antibacterial, and radical scavenging ability and good mechanical property to enhance full‐thickness skin wound regeneration is highly desirable in clinical application. Herein, a series of adhesive hemostatic antioxidant conductive photothermal antibacterial hydrogels based on hyaluronic acid‐graft‐dopamine and reduced graphene oxide (rGO) using a H₂O₂/HPR (horseradish peroxidase) system are prepared for wound dressing. These hydrogels exhibit high swelling, degradability, tunable rheological property, and similar or superior mechanical properties to human skin. The polydopamine endowed antioxidant activity, tissue adhesiveness and hemostatic ability, self‐healing ability, conductivity, and NIR irradiation enhanced in vivo antibacterial behavior of the hydrogels are investigated. Moreover, drug release and zone of inhibition tests confirm sustained drug release capacity of the hydrogels. Furthermore, the hydrogel dressings significantly enhance vascularization by upregulating growth factor expression of CD31 and improve the granulation tissue thickness and collagen deposition, all of which promote wound closure and contribute to a better therapeutic effect than the commercial Tegaderm films group in a mouse full‐thickness wounds model. In summary, these adhesive hemostatic antioxidative conductive hydrogels with sustained drug release property to promote complete skin regeneration are an excellent wound dressing for full‐thickness skin repair.     

Ultrastretchable and Wireless Bioelectronics Based on All‐Hydrogel Microfluidics

Hydrogel bioelectronics that can interface biological tissues and flexible electronics is at the core of the growing field of healthcare monitoring, smart drug systems, and wearable and implantable devices. Here, a simple strategy is demonstrated to prototype all‐hydrogel bioelectronics with embedded arbitrary conductive networks using tough hydrogels and liquid metal. Due to their excellent stretchability, the resultant all‐hydrogel bioelectronics exhibits stable electrochemical properties at large tensile stretch and various modes of deformation. The potential of fabricated all‐hydrogel bioelectronics is demonstrated as wearable strain sensors, cardiac patches, and near‐field communication (NFC) devices for monitoring various physiological conditions wirelessly. The presented simple platform paves the way of implantable hydrogel electronics for Internet‐of‐Things and tissue–machine interfacing applications.     

Ultrahigh‐Water‐Content,Superelastic, and Shape‐Memory Nanofiber‐Assembled Hydrogels Exhibiting Pressure‐Responsive Conductivity

High‐water‐content hydrogels that are both mechanically robust and conductive could have wide applications in fields ranging from bioengineering and electronic devices to medicine; however, creating such materials has proven to be extremely challenging. This study presents a scalable methodology to prepare superelastic, cellular‐structured nanofibrous hydrogels (NFHs) by combining alginate and flexible SiO₂ nanofibers. This approach causes naturally abundant and sustainable alginate to assemble into 3D elastic bulk NFHs with tunable water content and desirable shapes on a large scale. The resultant NFHs exhibit the integrated properties of ultrahigh water content (99.8 wt%), complete recovery from 80% strain, zero Poisson's ratio, shape‐memory behavior, injectability, and elastic‐responsive conductivity, which can detect dynamic pressure in a wide range (>50 Pa) with robust sensitivity (0.24 kPa^?1) and durability (100 cycles). The fabrication of such fascinating materials may provide new insights into the design and development of multifunctional hydrogels for various applications.     

Binary Synergistic Sensitivity Strengthening of Bioinspired Hierarchical Architectures based on Fragmentized Reduced Graphene Oxide Sponge and Silver Nanoparticles for Strain Sensors and Beyond

Recently, stretchable electronics have been highly desirable in the Internet of Things and electronic skins. Herein, an innovative and cost‐efficient strategy is demonstrated to fabricate highly sensitive, stretchable, and conductive strain‐sensing platforms inspired by the geometries of a spiders slit organ and a lobsters shell. The electrically conductive composites are fabricated via embedding the 3D percolation networks of fragmentized graphene sponges (FGS) in poly(styrene‐block‐butadiene‐block‐styrene) (SBS) matrix, followed by an iterative process of silver precursor absorption and reduction. The slit‐ and scale‐like structures and hybrid conductive blocks of FGS and Ag nanoparticles (NPs) provide the obtained FGS–Ag‐NP‐embedded composites with superior electrical conductivity of 1521 S cm^?1, high break elongation of 680%, a wide sensing range of up to 120% strain, high sensitivity of ≈10⁷ at a strain of 120%, fast response time of ≈20 ms, as well as excellent reliability and stability of 2000 cycles. This huge stretchability and sensitivity is attributed to the combination of high stretchability of SBS and the binary synergistic effects of designed FGS architectures and Ag NPs. Moreover, the FGS/SBS/Ag composites can be employed as wearable sensors to detect the modes of finger motions successfully, and patterned conductive interconnects for flexible arrays of light‐emitting diodes.     

Fabrication of Highly Stretchable Conductors via Morphological Control of Carbon Nanotube Network

Stretchable conductors, which can keep their excellent electrical conductivity while highly stretched, have been investigated extensively due to their wide range of applications in flexible and stretchable electronics, wearable displays, etc.; however, their preparation is often complicated and expensive. Herein, an efficient method to prepare high performance stretchable conductors through morphological control of conductive networks formed with carbon nanotubes (CNTs) in an elastomer matrix is reported. It is observed that an interface‐mediated method could be used to align randomly oriented filler during stretching and to induce buckling of CNTs during relaxation. Further morphological studies indicate the possible formation of a wavy CNT structure induced by cyclic pre‐straining. Subsequent thermal annealing is observed to collapse the oriented network and improve the local contacts between conductive networks. Through such a simple procedure, a conductivity of nearly 1000 S m^?1 and a stretchability of 200% can be achieved for composites containing 20 wt% CNTs. CNTs are observed to buckle over a large area in polymer bulk, and the combination of pre‐straining and thermal annealing modifies the conductive network in the elastomer matrix. As a general method, this could be used for easy fabrication of high‐performance stretchable conductors for arbitrary‐shaped objects on a large scale.     

Biofriendly,Stretchable, and Reusable Hydrogel Electronics as Wearable Force Sensors

The ever‐growing overlap between stretchable electronic devices and wearable healthcare applications is igniting the discovery of novel biocompatible and skin‐like materials for human‐friendly stretchable electronics fabrication. Amongst all potential candidates, hydrogels with excellent biocompatibility and mechanical features close to human tissues are constituting a promising troop for realizing healthcare‐oriented electronic functionalities. In this work, based on biocompatible and stretchable hydrogels, a simple paradigm to prototype stretchable electronics with an embedded three‐dimensional (3D) helical conductive layout is proposed. Thanks to the 3D helical structure, the hydrogel electronics present satisfactory mechanical and electrical robustness under stretch. In addition, reusability of stretchable electronics is realized with the proposed scenario benefiting from the swelling property of hydrogel. Although losing water would induce structure shrinkage of the hydrogel network and further undermine the function of hydrogel in various applications, the worn‐out hydrogel electronics can be reused by simply casting it in water. Through such a rehydration procedure, the dehydrated hydrogel can absorb water from the surrounding and then the hydrogel electronics can achieve resilience in mechanical stretchability and electronic functionality. Also, the ability to reflect pressure and strain changes has revealed the hydrogel electronics to be promising for advanced wearable sensing applications.     

Strong,Tough, and Anti-Swelling Supramolecular Conductive Hydrogels for Amphibious Motion Sensors

Conductive polymer hydrogels (CPHs) are widely employed in emerging flexible electronic devices because they possess both the electrical conductivity of conductors and the mechanical properties of hydrogels. However, the poor compatibility between conductive polymers and the hydrogel matrix, as well as the swelling behavior in humid environments, greatly compromises the mechanical and electrical properties of CPHs, limiting their applications in wearable electronic devices. Herein, a supramolecular strategy to develop a strong and tough CPH with excellent anti-swelling properties by incorporating hydrogen, coordination bonds, and cation-π interactions between a rigid conducting polymer and a soft hydrogel matrix is reported. Benefiting from the effective interactions between the polymer networks, the obtained supramolecular hydrogel has homogeneous structural integrity, exhibiting remarkable tensile strength (1.63 MPa), superior elongation at break (453%), and remarkable toughness (5.5 MJ m⁻³). As a strain sensor, the hydrogel possesses high electrical conductivity (2.16 S m⁻¹), a wide strain linear detection range (0–400%), and excellent sensitivity (gauge factor = 4.1), sufficient to monitor human activities with different strain windows. Furthermore, this hydrogel with high swelling resistance has been successfully applied to underwater sensors for monitoring frog swimming and underwater communication. These results reveal new possibilities for amphibious applications of wearable sensors.     

SMART Silly Putty: Stretchable,Malleable, Adherable,Reusable, and Tear-Resistible Hydrogels

Cell engineering, soft robotics, and wearable electronics often desire soft materials that are easy to deform, self-heal readily, and can relax stress rapidly. Hydrogels, a type of hydrophilic networks, are such kind of materials that can be made responsive to environmental stimuli. However, conventional hydrogels often suffer from poor stretchability and repairability. Here, hydrogels consisting of boronic ester dynamic covalent bonds in a double network of poly(vinyl alcohol)/boric acid and chitosan are synthesized, which demonstrate extreme stretchability (up to 310 times the original length), instant self-healing (within 5 s), and reusability and inherent adhesion. Their instant stress relaxation stems from a low activation energy of the boronic ester bond exchange (≤20 kJ mol⁻¹) and contributes to the extreme stretchability and self-healing behaviors. Various water-dispersible additives can be readily incorporated in the hydrogels via hand kneading for potential applications such as soft electronics, bio-signal sensing, and soft artificial joints.     

Tissue-Mimetic Supramolecular Polymer Networks for Bioelectronics

Addressing the mechanical mismatch between biological tissue and traditional electronic materials remains a major challenge in bioelectronics. While rigidity of such materials limits biocompatibility, supramolecular polymer networks can harmoniously interface with biological tissues as they are soft, wet, and stretchable. Here, an electrically conductive supramolecular polymer network that simultaneously exhibits both electronic and ionic conductivity while maintaining tissue-mimetic mechanical properties, providing an ideal electronic interface with the human body, is introduced. Rational design of an ultrahigh affinity host–guest ternary complex led to binding affinities (>10¹³ M^-2) of over an order of magnitude greater than previous reports. Embedding these complexes as dynamic cross-links, coupled with in situ synthesis of a conducting polymer, resulted in electrically conductive supramolecular polymer networks with tissue-mimetic Young's moduli (<5 kPa), high stretchability (>500%), rapid self-recovery and high water content (>84%). Achieving such properties enabled fabrication of intrinsically-stretchable stand-alone bioelectrodes, capable of accurately monitoring electromyography signals, free from any rigid materials.     

高强度聚苯胺-聚丙烯酸/聚丙烯酰胺导电水凝胶的制备与性能

将导电聚合物引入到水凝胶网络中的导电高分子基导电水凝胶,因结合了水凝胶的三维网络结构、良好的生物相容性、优异的力学性能等和导电高分子良好电学性能等优点而被广泛研究,特别是以聚苯胺(PANI)为导电高分子的导电水凝胶。但PANI不溶于水,因此很难制备PANI基导电水凝胶。本文以制备高强度PANI基导电水凝胶为目的,尝试将PANI接枝在亲水性聚合物聚丙烯酸(PAA)上,获得能在水中均匀分散的PANI-PAA导电复合物,再使其与丙烯酰胺(AM)聚合得到高强度的PANI-PAA/PAM导电水凝胶。通过力学性能及电化学性能测试,发现该导电水凝胶具有良好的力学性能和电化学性能。当以十二烷基硫酸钠(SDS)为分散剂时,其电导率可达4.63 S·m?1,可承受压缩应力1.33 MPa (压缩耗散能为85.50 kJ·m?3),拉伸断裂伸长率达964%,相应的断裂强度为0.25 MPa;而以NaOH为分散剂时,凝胶的电导率可达4.19 S·m?1,可承受压缩应力1.13 MPa (压缩耗散能为73.45 kJ·m?3),拉伸断裂伸长率达896%;相应的断裂强度为 0.14 MPa。该研究为高强度聚苯胺基导电水凝胶的制备提供了思路。      

Highly Stretchable,Compliant, Polymeric Microelectrode Arrays for In Vivo Electrophysiological Interfacing

Polymeric microelectrode arrays (MEAs) are emerging as a new generation of biointegrated microelectrodes to transduce original electrochemical signals in living tissues to external electrical circuits, and vice versa. So far, the challenge of stretchable polymeric MEAs lies in the competition between high stretchability and good electrode–substrate adhesion. The larger the stretchability, the easier the delamination of electrodes from the substrate due to the mismatch in their Young's modulus. In this work, polypyrrole (PPy) electrode materials are designed, with PPy nanowires integrated on the high conductive PPy electrode arrays. By utilizing this electrode material, for the first time, stretchable polymeric MEAs are fabricated with both high stretchability (≈100%) and good electrode–substrate adhesion (1.9 MPa). In addition, low Young's modulus (450 kPa), excellent recycling stability (10 000 cycles of stretch), and high conductivity of the MEAs are also achieved. As a proof of concept, the as‐prepared polymeric MEAs are successfully used for conformally recording the electrocorticograph signals from rats in normal and epileptic states, respectively. Further, these polymeric MEAs are also successful in stimulating the ischiadic nerve of the rat. This strategy provides a new perspective to the highly stretchable and mechanically stable polymeric MEAs, which are vital for compliant neural electrodes.     

Skin‐Inspired Multifunctional Autonomic‐Intrinsic Conductive Self‐Healing Hydrogels with Pressure Sensitivity,Stretchability, and 3D Printability

The advent of conductive self‐healing (CSH) hydrogels, a class of novel materials mimicking human skin, may change the trajectory of the industrial process because of their potential applications in soft robots, biomimetic prostheses, and health‐monitoring systems. Here, the development of a mechanically and electrically self‐healing hydrogel based on physically and chemically cross‐linked networks is reported. The autonomous intrinsic self‐healing of the hydrogel is attained through dynamic ionic interactions between carboxylic groups of poly(acrylic acid) and ferric ions. A covalent cross‐linking is used to support the mechanical structure of the hydrogel. Establishing a fair balance between the chemical and physical cross‐linking networks together with the conductive nanostructure of polypyrrole networks leads to a double network hydrogel with bulk conductivity, mechanical and electrical self‐healing properties (100% mechanical recovery in 2 min), ultrastretchability (1500%), and pressure sensitivity. The practical potential of CSH hydrogels is further revealed by their application in human motion detection and their 3D‐printing performance.     

Material Design and Fabrication Strategies for Stretchable Metallic Nanocomposites

Stretchable conductive nanocomposites fabricated by integrating metallic nanomaterials with elastomers have become a vital component of human‐friendly electronics, such as wearable and implantable devices, due to their unconventional electrical and mechanical characteristics. Understanding the detailed material design and fabrication strategies to improve the conductivity and stretchability of the nanocomposites is therefore important. This Review discusses the recent technological advances toward high performance stretchable metallic nanocomposites. First, the effect of the filler material design on the conductivity is briefly discussed, followed by various nanocomposite fabrication techniques to achieve high conductivity. Methods for maintaining the initial conductivity over a long period of time are also summarized. Then, strategies on controlled percolation of nanomaterials are highlighted, followed by a discussion regarding the effects of the morphology of the nanocomposite and postfabricated 3D structures on achieving high stretchability. Finally, representative examples of applications of such nanocomposites in biointegrated electronics are provided. A brief outlook concludes this Review.     

Fully Integrated Design of a Stretchable Solid‐State Lithium‐Ion Full Battery

A solid‐state lithium‐ion battery, in which all components (current collector, anode and cathode, electrolyte, and packaging) are stretchable, is introduced, giving rise to a battery design with mechanical properties that are compliant with flexible electronic devices and elastic wearable systems. By depositing Ag microflakes as a conductive layer on a stretchable carbon–polymer composite, a current collector with a low sheet resistance of ≈2.7 Ω □^?1 at 100% strain is obtained. Stretchable electrodes are fabricated by integrating active materials with the elastic current collector. A polyacrylamide–“water‐in‐salt” electrolyte is developed, offering high ionic conductivity of 10^?3 to 10^?2 S cm^?1 at room temperature and outstanding stretchability up to ≈300% of its original length. Finally, all these components are assembled into a solid‐state lithium‐ion full cell in thin‐film configuration. Thanks to the deformable individual components, the full cell functions when stretched, bent, or even twisted. For example, after stretching the battery to 50%, a reversible capacity of 28 mAh g^?1 and an average energy density of 20 Wh kg^?1 can still be obtained after 50 cycles at 120 mA g^?1, confirming the functionality of the battery under extreme mechanical stress.     

Flexible,Stretchable, and Transparent Planar Microsupercapacitors Based on 3D Porous Laser‐Induced Graphene

The graphene with 3D porous network structure is directly laser‐induced on polyimide sheets at room temperature in ambient environment by an inexpensive and one‐step method, then transferred to silicon rubber substrate to obtain highly stretchable, transparent, and flexible electrode of the all‐solid‐state planar microsupercapacitors. The electrochemical capacitance properties of the graphene electrodes are further enhanced by nitrogen doping and with conductive poly(3,4‐ethylenedioxythiophene) coating. With excellent flexibility, stretchability, and capacitance properties, the planar microsupercapacitors present a great potential in fashionable and comfortable designs for wearable electronics.     

Reduced Graphene Oxide‐GelMA Hybrid Hydrogels as Scaffolds for Cardiac Tissue Engineering

Biomaterials currently used in cardiac tissue engineering have certain limitations, such as lack of electrical conductivity and appropriate mechanical properties, which are two parameters playing a key role in regulating cardiac cell behavior. Here, the myocardial tissue constructs are engineered based on reduced graphene oxide (rGO)‐incorporated gelatin methacryloyl (GelMA) hybrid hydrogels. The incorporation of rGO into the GelMA matrix significantly enhances the electrical conductivity and mechanical properties of the material. Moreover, cells cultured on composite rGO‐GelMA scaffolds exhibit better biological activities such as cell viability, proliferation, and maturation compared to ones cultured on GelMA hydrogels. Cardiomyocytes show stronger contractility and faster spontaneous beating rate on rGO‐GelMA hydrogel sheets compared to those on pristine GelMA hydrogels, as well as GO‐GelMA hydrogel sheets with similar mechanical property and particle concentration. Our strategy of integrating rGO within a biocompatible hydrogel is expected to be broadly applicable for future biomaterial designs to improve tissue engineering outcomes. The engineered cardiac tissue constructs using rGO incorporated hybrid hydrogels can potentially provide high‐fidelity tissue models for drug studies and the investigations of cardiac tissue development and/or disease processes in vitro.