Development of conductive hydrogels: from design mechanisms to frontier applications

Owing to their excellent mechanical flexibility, electrical conductivity, and biocompatibility, conductive hydrogels(CHs) are widely used in the fields of energy and power, and biomedical technology. To arrive at a better understanding of the design methods and development trends of CHs, this paper summarizes and analyzes related research published in recent years. First,we describe the properties and characteristics of CHs. Using Scopus, the world’s largest abstract and citation database, we conducted a quantitative analysis of the related literature from the past 15 years and summarized development trends in the field of CHs. Second, we describe the types of CH network crosslinking and basic functional design methods and summarize the three-dimensional(3D) structure-forming methods and conductive performance tests of CHs. In addition, we introduce applications of CHs in the fields of energy and power, biomedical technology, and others. Lastly, we discuss several problems in current CH research and introduce some prospects for the future development of CHs.

Hybrid assembly of conducting nanofiber network for ultra-stretchable and highly sensitive conductive hydrogels

Conductive hydrogels have attracted extensive attention owing to their promising application prospects in flexible and wearable electronics.However,achieving both high sensitivity and mechanical robustness remains challenging.Herein,a novel and versatile conductive hydrogel based on the hybrid assem-bly of conductive cellulose nanofiber(CNF)networks has been designed and fabricated.Assisted by the templating effect of CNFs and stabilizing effect of negatively charged poly(styrene sulfonate)(PSS),conducting polymer poly(3,4-ethylenedioxythiophene)(PEDOT)was self-organized into three-dimensional nanostructures which constructed a robust conductive network after in-situ oxidative polymerization.The unique structure derived from CNF bio-template endowed polyacrylamide(PAM)hydrogels with improved electrical conductivity and excellent mechanical performance.As a result,the as-fabricated CNF/PEDOT:PSS/PAM hydrogel exhibited an ultimate tensile strain of 1881%and toughness of 3.72 MJ/m^(3),which were 4.07 and 8.27 times higher than the CNF-free hydrogel,respectively.More significantly,the resultant hydrogel sensor showed highly desirable sensing properties,including remarkable sensing range(1100%),high gauge factor(GF=5.16),fast response time(185 ms),and commendable durability,as well as good adhesiveness.Moreover,the hydrogel sensor was able to distinguish subtle physiological activities including phonation and facial expression,and monitor large human body motions such as finger flexion and elbow blending.Besides,it was feasible to integrate the strain sensor on the joints of robots to recognize complicated machine motion signals,showing potential in advanced human-machine interactions.

Conductive hydrogels incorporating carbon nanoparticles:A review of synthesis,performance and applications

As one of the most rapidly expanding materials,hydrogels have gained increasing attention in a variety of fields due to their biocompatibility,degradability and hydrophilic properties,as well as their remarkable adhesion and stretchability to adapt to different surfaces.Hydrogels combined with carbon-based materials possess enhanced properties and new functionalities,in particular,conductive hydrogels have become a new area of research in the field of materials science.This review aims to provide a comprehensive overview and up-to-date examination of recent developments in the synthesis,properties and applications of conductive hydrogels incorporating several typical carbon nanoparticles such as carbon nanotubes,graphene,carbon dots and carbon nanofibers.We summarize key techniques and mechanisms for synthesizing various composite hydrogels with exceptional properties,and represented applications such as wearable sensors,temperature sensors,supercapacitors and human-computer interaction reported recently.The mechanical,electrical and sensing properties of carbon nanoparticles conductive hydrogels are thoroughly analyzed to disclose the role of carbon nanoparticles in these hydrogels and key factors in the microstructure.Finally,future development of conductive hydrogels based on carbon nanoparticles is discussed including the challenges and possible solutions in terms of microstructure optimization,mechanical and other properties,and promising applications in wearable electronics and multifunctional materials.

Recent advances in designing conductive hydrogels for flexible electronics

Flexible electronics have emerged as an exciting research area in recent years,serving as ideal interfaces bridging biological systems and conventional electronic devices.Flexible electronics can not only collect physiological signals for human health monitoring but also enrich our daily life with multifunctional smart materials and devices.Conductive hydrogels(CHs)have become promising candidates for the fabrication of flexible electronics owing to their biocompatibility,adjustable mechanical flexibility,good conductivity,and multiple stimuli-responsive properties.To achieve on-demand mechanical properties such as stretchability,compressibility,and elasticity,the rational design of polymer networks via modulating chemical and physical intermolecular interactions is required.Moreover,the type of conductive components(eg,electron-conductive materials,ions)and the incorporation method also play an important role in the conductivity of CHs.Electron-CHs usually possess excellent conductivity,while ion-CHs are generally transparent and can generate ion gradients within the hydrogel matrices.This mini review focuses on the recent advances in the design of CHs,introducing various design strategies for electron-CHs and ion-CHs employed in flexible electronics and highlighting their versatile applications such as biosensors,batteries,supercapacitors,nanogenerators,actuators,touch panels,and displays.

Tough,conductive hydrogels with double-network based on hydrophilic polymer assistant well-dispersed carbon nanotube for innovative force sensor

In recent years,conductive hydrogels have become a promising candidate for application in fields such as tissue engineering and flexible electronic devices because of their conductivity,soft and wet nature.However,the preparation of tough and uniformly conductive hydrogels remains challenging because conductive nanofillers tend to aggregate during hydrogel formation.Herein,a hydrophilic polymer assistant dispersion strategy is proposed to fabricate a tough,conductive composite hydrogel with doublenetwork based on well-dispersed carbon nanotubes(CNTs).In particular,A@T_(2.0)/polyacrylamide(PAM)hydrogels showed a tensile strength of 332.9 kPa,elongation of 584.6%,Young’s modulus of 91.5 kPa,and conductivity of 2.765 S m^(-1),and a demonstration was performed to show the strain sensing for health monitoring and handwriting.Results showed that the fabricated conductive hydrogels offer promising and broad insights in the field of wearable sensors for health monitoring,innovative electronics,and human-machine interactions.

Ionic conductive hydrogels toughened by latex particles for strain sensors

Conductive hydrogels have attracted tremendous attention due to their excellent softness and stretchability as wearable strain sensing devices.However,most of hydrogel-based strain sensors suffered from poor self-recoverability and fatigue resistance,resulting in significant decrease of strain sensitivity after recycling.Here,a soft and flexible wearable strain sensor is prepared by using an ionic conductive hydrogel with latex particles as physical cross-linking centers.The dynamic physical cross-linking structure can effectively dissipate energy through disruption and reconstruction of molecular segments,thereby imparting excellent stretchability,self-recoverability and fatigue resistance.In addition,the hydrogel exhibits excellent strain-sensitive resistance changes,which enables it to be assembled as a wearable sensor to monitor human motions.As a result,the hydrogel strain sensor can provide precise feedback for a wide range of human activities,including large-scale joint bending and tiny phonating.Therefore,the tough ionic conductive hydrogel would be widely applied in electronic skin,medical monitoring and artificial intelligence.

Preparation and Performance Study of PVA-Based Flexible Sensors

Flexible sensors have great potential for monitoring human body motion signals. This paper presents a flexible sensor that uses zinc oxide (ZnO) to improve the mechanical properties and electrical conductivity of PVA hydrogel. The composite hydrogel has excellent conductive properties and high strain sensitivity, making it suitable for motion monitoring. The PVA/ZnO conductive hydrogel is tested on various body parts, showing effective feedback on movement changes and good electrical signal output effects for different motion degrees, confirming its feasibility in flexible sensors. The sensor exhibits good mechanical properties, electrical conductivity, and tensile strain sensing performance, making it a promising sensor material. It can accurately monitor wrist bending, finger deformation, bending, and large-scale joint movements due to its wide monitoring range and recoverable strain. The results show that the PVA/ZnO conductive hydrogel can provide effective feedback in flexible sensors, which is suitable for use in motion monitoring.

Mussel‑Inspired Redox‑Active and Hydrophilic Conductive Polymer Nanoparticles for Adhesive Hydrogel Bioelectronics

Conductive polymers(CPs)are generally insoluble,and developing hydrophilic CPs is significant to broaden the applications of CPs.In this work,a mussel-inspired strategy was proposed to construct hydrophilic CP nanoparticles(CP NPs),while endowing the CP NPs with redox activity and biocompatibility.This is a universal strategy applicable for a series of CPs,including polyaniline,polypyrrole,and poly(3,4-ethylenedioxythiophene).The catechol/quinone contained sulfonated lignin(LS)was doped into various CPs to form CP/LS NPs with hydrophilicity,conductivity,and redox activity.These CP/LS NPs were used as versatile nanofillers to prepare the conductive hydrogels with long-term adhesiveness.The CP/LS NPs-incorporated hydrogels have a good conductivity because of the uniform distribution of the hydrophilic NPs in the hydrogel network,forming a well-connected electric path.The hydrogel exhibits long-term adhesiveness,which is attributed to the mussel-inspired dynamic redox balance of catechol/quinone groups on the CP/LS NPs.This conductive and adhesive hydrogel shows good electroactivity and biocompatibility and therefore has broad applications in electrostimulation of tissue regeneration and implantable bioelectronics.

Transparent,Ultra-Stretching,Tough,Adhesive Carboxyethyl Chitin/Polyacrylamide Hydrogel Toward High-Performance Soft Electronics

To date,hydrogels have gained increasing attentions as a flexible conductive material in fabricating soft electronics.However,it remains a big challenge to integrate multiple functions into one gel that can be used widely under various conditions.Herein,a kind of multifunc-tional hydrogel with a combination of desirable characteristics,including remarkable transparency,high conductivity,ultra-stretchability,tough-ness,good fatigue resistance,and strong adhesive ability is presented,which was facilely fabricated through multiple noncovalent crosslinking strategy.The resultant versatile sensors are able to detect both weak and large deformations,which owns a low detection limit of 0.1%strain,high stretchability up to 1586%,ultrahigh sensitivity with a gauge factor up to 18.54,as well as wide pressure sensing range(0-600 kPa).Meanwhile,the fabrication of conductive hydrogel-based sensors is demonstrated for various soft electronic devices,including a flexible human-machine interactive system,the soft tactile switch,an integrated electronic skin for unprecedented nonplanar visualized pressure sensing,and the stretchable triboelectric nanogenerators with excellent biomechanical energy harvesting ability.This work opens up a simple route for multifunctional hydrogel and promises the practical application of soft and self-powered wearable electronics in various complex scenes.

An integrated portable bio-monitoring system based on tough hydrogels for comprehensive detection of physiological activities

Advanced soft ion-conducting hydrogels have been developed rapidly in the integrated portable health monitoring equipment due to their higher sensitivity,sensory traits,tunable conductivity,and stretchability for physiological activities and personal healthcare detection.However,traditional hydrogel conductors are normally susceptible to large deformation and strong mechanical stress,which leads to inferior electro-mechanical stability for real application scenarios.Herein,a strong ionically conductive hydrogel(poly(vinyl alcohol)-boric acid-glycerol/sodium alginate-calcium chloride/electrolyte ions(PBG/SC/EI))was designed by engineering the covalently and ionically crosslinked networks followed by the salting-out effect to further enhance the mechanical strength and ionic conductivity of the hydrogel.Owing to the collective effects of the energy-dissipation mechanism and salting-out effect,the designed PBG/SC/EI with excellent structural integrity and robustness exhibits exceptional mechanical properties(elongation at break for 559.1%and tensile strength of 869.4 kPa)and high ionic conductivity(1.618 S·m^(-1)).As such,the PBG/SC/EI strain sensor features high sensitivity(gauge factor=2.29),which can effectively monitor various kinds of human motions(joint motions,facial micro-expression,faint respiration,and voice recognition).Meanwhile,the hydrogel-based Zn||MnO_(2)battery delivers a high capacity of 267.2 mAh·g^(-1)and a maximal energy density of 356.8 Wh·kg^(-1)associated with good cycle performance of 71.8%capacity retention after 8000 cycles.Additionally,an integrated bio-monitoring system with the sensor and Zn||MnO_(2)battery can accurately identify diverse physiological activities in a real-time and non-invasive way.This work presents a feasible strategy for designing high-performance conductive hydrogels for highly-reliable integrated bio-monitoring systems with excellent practicability.

Bioinspired anti-freezing 3D-printable conductive hydrogel microfibers for highly-sensitive and wide-range detection of ultralow and high strains

Soft strain sensors that can transduce stretch stimuli into electrical readouts are promising as sustainable wearable electronics.However,most strain sensors cannot achieve highly-sensitive and wide-range detection of ultralow and high strains.Inspired by bamboo structures,anti-freezing microfibers made of conductive poly(vinyl alcohol)hydrogel with poly(3,4-ethylenedioxythiphene)-poly(styrenesulfonate)are developed via continuous microfluidic spinning.The microfibers provide unique bamboo-like structures with enhanced local stress to improve both their length change and resistance change upon stretching for efficient signal conversion.The microfibers allow highlysensitive(detection limit:0.05%strain)and wide-range(0%-400%strain)detection of ultralow and high strains,as well as features of good stretchability(485%strain)and anti-freezing property(freezing temperature:-41.1°C),fast response(200 ms),and good repeatability.The experimental results,together with theoretical foundation analysis and finite element analysis,prove their enhanced length and resistance changes upon stretching for efficient signal conversion.By integrating microfluidic spinning with 3D-printing technique,the textiles of the microfibers can be flexibly constructed.The microfibers and their 3D-printed textiles enable highperformance monitoring of human motions including finger bending and throat vibrating during phonation.This work provides an efficient and general strategy for developing advanced conductive hydrogel microfibers as highperformance wearable strain sensors.

Conductive ionic liquid/chitosan hydrogels for neuronal cell differentiation

To regulate cell behaviors and promote nerve function recovery,three-dimensional(3D)conductive hydrogel can transmit intercellular electrical signals,and effectively provide the cell survival environment.However,produc-ing hydrogels with simultaneous high conductivity,favorable biocompatibility,and tissue-matching properties remains a challenge for spinal cord injury(SCI)treatment.Here,a conductive,multifunctional,and biocompati-ble VPImBF4 ionic liquid(IL)with photosensitive chitosan-based hydrogel(pCM@IL)is developed.The pCM@IL hydrogel exhibits a 3D microporous structure that could maintain cell viability and improve cell growth.Elas-tic modulus,conductivity,and biodegradability of the pCM@IL hydrogels are investigated with tissue-matching mechanical properties.The pCM@IL conductive hydrogels synergistically enhance neuronal cell proliferation and promote neuronal cells differentiation via upregulates synapse gene(Tubulin𝛽3,GAP43,Synaptophysin)expression.Furthermore,in vivo studies of the pCM@IL conductive hydrogels as implants demonstrate low-inflammation and neovascularize promotion and appropriate biodegradable properties.The developed pCM@IL conductive hydrogel is a promising therapeutic scaffold biomaterial for SCI repair.

A shape-persistent plasticine-like conductive hydrogel with self-healing properties for peripheral nerve regeneration

In recent years,electrically conductive hydrogel-based nerve guidance conduits(NGCs)have yielded promising results for treating peripheral nerve injuries(PNIs).However,developed ones are generally pre-manufactured and exhibit a limited ability to achieve good contact with nerve tissue with irregu-lar surfaces.Herein,we developed a plasticine-like electrically conductive hydrogel consisting of gelatin,conducting polypyrrole,and tannic acid(named GPT)and assessed its ability to promote peripheral nerve regeneration.The shape-persistent GPT hydrogel exhibited good self-healing properties and could easily be molded to form a conduit that could match any injured nerve tissue.Their electrical properties could be tuned by changing the PPy concentration.In vitro,the improved conductivity of the hydrogel pro-moted dorsal root ganglion(DRG)axonal extension.More importantly,we found that the GPT hydrogel enhanced axonal regeneration and remyelination in vivo,preventing denervation atrophy and enhancing functional recovery in a mice model of sciatic nerve injury.These results suggest that our plasticine-like NGC has huge prospects for clinical application in the repair of PNI.

Real-time monitoring flexible hydrogels based on dual physically cross-linked network for promoting wound healing

To achieve smart and personalized medicine, the development of hydrogel dressings with sensing properties and biotherapeutic properties that can act as a sensor to monitor of human health in real-time while speeding up wound healing face great challenge. In the present study, a biocompatible dual-network composite hydrogel(DNCGel) sensor was obtained via a simple process. The dual network hydrogel is constructed by the interpenetration of a flexible network formed of poly(vinyl alcohol)(PVA) physical cross-linked by repeated freeze-thawing and a rigid network of iron-chelated xanthan gum(XG) impregnated with Fe^(3+) interpenetration. The pure PVA/XG hydrogels were chelated with ferric ions by immersion to improve the gel strength(compressive modulus and tensile modulus can reach up to 0.62 MPa and0.079 MPa, respectively), conductivity(conductivity values ranging from 9 × 10^(-4) S/cm to 1 × 10^(-3)S/cm)and bacterial inhibition properties(up to 98.56%). Subsequently, the effects of the ratio of PVA and XG and the immersion time of Fe^(3+) on the hydrogels were investigated, and DNGel3 was given the most priority on a comprehensive consideration. It was demonstrated that the DNCGel exhibit good biocompatibility in vitro, effectively facilitate wound healing in vivo(up to 97.8% healing rate) under electrical stimulation, and monitors human movement in real time. This work provides a novel avenue to explore multifunctional intelligent hydrogels that hold great promise in biomedical fields such as smart wound dressings and flexible wearable sensors.

Highly sensitive flexible strain sensor based on microstructured biphasic hydrogels for human motion monitoring

Flexible strain sensors have been extensively used in human motion detection,medical aids,electronic skins,and other civilian or military fields.Conventional strain sensors made of metal or semiconductor materials suffer from insufficient stretchability and sensitivity,imposing severe constraints on their utilization in wearable devices.Herein,we design a flexible strain sensor based on biphasic hydrogel via an in-situ polymerization method,which possesses superior electrical response and mechanical performance.External stress could prompt the formation of conductive microchannels within the biphasic hydrogel,which originates from the interaction between the conductive water phase and the insulating oil phase.The device performance could be optimized by carefully regulating the volume ratio of the oil/water phase.Consequently,the flexible strain sensor with oil phase ratio of 80%demonstrates the best sensitivity with gauge factor of 33 upon a compressive strain range of 10%,remarkable electrical stability of 100 cycles,and rapid resistance response of 190 ms.Furthermore,the human motions could be monitored by this flexible strain sensor,thereby highlighting its potential for seamless integration into wearable devices.

Self-sensing magnetic actuators of bilayer hydrogels

Hard magnetic soft robots have been widely used in biomedical engineering.In these applications,it is crucial to sense the movement of soft robots and their interaction with target objects.Here,we propose a strategy to fabricate a self-sensing bilayer actuator by combining magnetic and ionic conductive hydrogels.The magnetic hydrogel containing NdFeB particles exhibits rapid response to magnetic field and achieve bending deformation.Meanwhile,the polyacrylamide(PAAm)hydrogel with lithium chloride(LiCl)allows for the sensing of deformation.The bending behavior of the bilayer under magnetic field is well captured by theoretical and simulated models.Additionally,the bilayer strain sensor shows good sensitivity,stability and can endure a wide-range cyclic stretching(0-300%).These merits qualify the self-sensing actuator to monitor the motion signals,such as bending of fingers and grasping process of an intelligent gripper.When subject to an external magnetic field,the gripper can grab a cube and sense the resistance change simultaneously to detect the object size.This work may provide a versatile strategy to integrate actuating and self-sensing ability in soft robots.

Mussel-inspired nanozyme catalyzed conductive and self-setting hydrogel for adhesive and antibacterial bioelectronics

Adhesive hydrogels have broad applications ranging from tissue engineering to bioelectronics;however,fabricating adhesive hydrogels with multiple functions remains a challenge.In this study,a mussel-inspired tannic acid chelated-Ag(TA-Ag)nanozyme with peroxidase(POD)-like activity was designed by the in situ reduction of ultrasmall Ag nanoparticles(NPs)with TA.The ultrasmall TA-Ag nanozyme exhibited high catalytic activity to induce hydrogel self-setting without external aid.The nanozyme retained abundant phenolic hydroxyl groups and maintained the dynamic redox balance of phenol-quinone,providing the hydrogels with long-term and repeatable adhesiveness,similar to the adhesion of mussels.The phenolic hydroxyl groups also afforded uniform distribution of the nanozyme in the hydrogel network,thereby improving its mechanical properties and conductivity.Furthermore,the nanozyme endowed the hydrogel with antibacterial activity through synergistic effects of the reactive oxygen species generated via POD-like catalytic reactions and the intrinsic bactericidal activity of Ag.Owing to these advantages,the ultrasmall TA-Ag nanozyme-catalyzed hydrogel could be effectively used as an adhesive,antibacterial,and implantable bioelectrode to detect bio-signals,and as a wound dressing to accelerate tissue regeneration while preventing infection.Therefore,this study provides a promising approach for the fabrication of adhesive hydrogel bioelectronics with multiple functions via mussel-inspired nanozyme catalysis.

3D bioprinting of conductive hydrogel for enhanced myogenic differentiation

Recently,hydrogels have gained enormous interest in three-dimensional(3D)bioprinting toward developing functional substitutes for tissue remolding.However,it is highly challenging to transmit electrical signals to cells due to the limited electrical conductivity of the bioprinted hydrogels.Herein,we demonstrate the 3D bioprinting-assisted fabrication of a conductive hydrogel scaffold based on poly-3,4-ethylene dioxythiophene(PEDOT)nanoparticles(NPs)deposited in gelatin methacryloyl(GelMA)for enhanced myogenic differentiation of mouse myoblasts(C2C12 cells).Initially,PEDOT NPs are dispersed in the hydrogel uniformly to enhance the conductive property of the hydrogel scaffold.Notably,the incorporated PEDOT NPs showed minimal influence on the printing ability of GelMA.Then,C2C12 cells are successfully encapsulated within GelMA/PEDOT conductive hydrogels using 3D extrusion bioprinting.Furthermore,the proliferation,migration and differentiation efficacies of C2C12 cells in the highly conductive GelMA/PEDOT composite scaffolds are demonstrated using various in vitro investigations of live/dead staining,F-actin staining,desmin and myogenin immunofluorescence staining.Finally,the effects of electrical signals on the stimulation of the scaffolds are investigated toward the myogenic differentiation of C2C12 cells and the formation of myotubes in vitro.Collectively,our findings demonstrate that the fabrication of the conductive hydrogels provides a feasible approach for the encapsulation of cells and the regeneration of the muscle tissue.

Capacitance Performances of Supramolecular Hydrogels Based on Conducting Polymers

The capacitance performances of poly（3,4-ethylenedioxythiophene）-poly（styrenesulfonate）（PEDOT-PSS） supramolecular hydrogels have been investigated systematically. The materials show a specific capacitance of 67 F/g and display excellent rate capability at the scan rate as high as 5000 m V/s in the cyclic voltammogram measurements, accompanied by good cycle stability. On the basis of the measurements of the microscale morphologies, specific areas and electrical conductivities, the mechanisms for the improvement of the electrochemical properties are discussed and ascribed to the novel porous microstructures of the hydrogels and the synergetic effect of the rigid PEDOT and soft PSS components. Furthermore, polyaniline（PAn） is compounded with the PEDOT-PSS hydrogels through an interfacial polymerization process, endowing the hydrogel materials with a higher specific capacitance of 160 F/g at the scan rate of 5000 m V/s. The significance of this work lies in the demonstration of a novel method to solve the problems of conducting polymers in electrochemical applications.

Minimally invasive bioprinting for in situ liver regeneration

In situ bioprinting is promising for developing scaffolds directly on defect models in operating rooms,which provides a new strategy for in situ tissue regeneration.However,due to the limitation of existing in situ biofabrication technologies including printing depth and suitable bioinks,bioprinting scaffolds in deep dermal or extremity injuries remains a grand challenge.Here,we present an in vivo scaffold fabrication approach by minimally invasive bioprinting electroactive hydrogel scaffolds to promote in situ tissue regeneration.The minimally invasive bioprinting system consists of a ferromagnetic soft catheter robot for extrusion,a digital laparoscope for in situ monitoring,and a Veress needle for establishing a pneumoperitoneum.After 3D reconstruction of the defects with computed tomography,electroactive hydrogel scaffolds are printed within partial liver resection of live rats,and in situ tissue regeneration is achieved by promoting the proliferation,migration,and differentiation of cells and maintaining liver function in vivo.