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Although conductive hydrogel-based flexible electronic devices have superb flexibility and high conductivities, they tend to malfunction in dry or frigid areas. Herein, an ultralow-temperature tolerant, antidrying, and conductive composite hydrogel is designed for electronic skin applications on the basis of the synergy of double-cross-linked polymer networks, Hofmeister effect, and electrostatic interaction and fabricated by in situ free radical polymerization of 2-acrylamido-2-methyl-1-propanesulfonic acid and acrylic acid in the presence of poly(vinyl alcohol) and conductive MXene sheets, followed by impregnation with LiCl. Thanks to the synergy of LiCl and the charged polar terminal groups of the synthesized polymers, the composite hydrogel can not only bear an ultralow temperature of -80 °C without freezing but also maintain its original mass. Meanwhile, the resultant hydrogel possesses satisfactory self-regeneration ability benefiting from the moisturizing effect of LiCl. The conductive network of MXene sheets greatly improves the ionic conductivity of the hydrogel at low temperatures, exhibiting an ionic conductivity of 1.4 S m-1 at -80 °C. Furthermore, the electronic skin assembled by the multifunctional hydrogel is efficient in monitoring human motions at -80 °C. The antifreezing and antidrying features along with favorable ionic conductivity, high tensile strength, and outstanding flexibility make the composite hydrogel promising for applications in frigid and dry regions.
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Hydrogels are soft-wet materials with a hydrophilic three-dimensional network structure offering controllable stretchability, conductivity, and biocompatibility. However, traditional conductive hydrogels only operate in mild environments and exhibit poor environmental tolerance due to their high water content and hydrophilic network, which result in undesirable swelling, susceptibility to freezing at sub-zero temperatures, and structural dehydration through evaporation. The application range of conductive hydrogels is significantly restricted by these limitations. Therefore, developing environmentally tolerant conductive hydrogels (ETCHs) is crucial to increasing the application scope of these materials. In this review, we summarize recent strategies for designing multifunctional conductive hydrogels that possess anti-freezing, anti-drying, and anti-swelling properties. Furthermore, we briefly introduce some of the applications of ETCHs, including wearable sensors, bioelectrodes, soft robots, and wound dressings. The current development status of different types of ETCHs and their limitations are analyzed to further discuss future research directions and development prospects.
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Although conductive hydrogels (CHs) have been investigated as the wearable sensor in recent years, how to prepare the multifunctional CHs with long-term usability is still a big challenge. In this paper, we successfully prepared a kind of conductive and self-adhesive hydrogel with a simple method, and its excellent ductility makes it possible as a flexible strain sensor for intelligent monitoring. The CHs are constructed by poly(vinyl alcohol) (PVA), polydopamine (PDA), and phytic acid (PA) through the freeze-thaw cycle method. The introduction of PA enhanced the intermolecular force with PVA and provided much H+ for augmented conductivity, while the catechol group on PDA endows the hydrogel with self-adhesion ability. The PVA/PA/PDA hydrogel can directly contact with the skin and adhere to it stably, which makes the hydrogel potentially a wearable strain sensor. The PVA/PA/PDA hydrogel can monitor human motion signals (including fingers, elbows, knees, etc.) in real-time and can accurately monitor tiny electrical signals for smile and handwriting recognition. Notably, the composite CHs can be used in a normal environment even after 4 months. Because of its excellent ductility, self-adhesiveness, and conductivity, the PVA/PA/PDA hydrogel provides a new idea for wearable bioelectronic sensors.
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Adhesivos , Hidrogeles , Humanos , Cementos de Resina , Conductividad Eléctrica , Adhesividad , Ácido FíticoRESUMEN
Conductive hydrogels have attracted tremendous interest in the construction of flexible strain sensors and triboelectric nanogenerators (TENGs) owing to their good stretchability and adjustable properties. Nevertheless, how to simultaneously achieve high transparency, self-healing, adhesion, antibacterial, anti-freezing, anti-drying, and biocompatibility properties through a simple method remains a challenge. Herein, a transparent, freezing-tolerant, and multifunctional organohydrogel (PAOAM-PDO) as electrode for strain sensors and TENGs was constructed through a free radical polymerization in the 1,3-propanediol (PDO)/water binary solvent system, in which oxide sodium alginate, aminated gelatin, acrylic acid, and AlCl3 were used as raw materials. The obtained PAOAM-PDO exhibited good transparency (>90%), self-healing, adhesiveness, antibacterial property, good conductivity (1.13 S/m), and long-term environmental stability. The introduction of PDO endowed PAOAM-PDO with freezing resistance with a low freezing point of -60 °C, and PAOAM-PDO could serve as a protective skin barrier to prevent frostbite at low temperature. PAOAM-PDO could be assembled as strain sensors to monitor heterogeneous human movements with high strain sensitivity (gauge factor of 7.05, strain = 233%). Meanwhile, PAOAM-PDO could be further fabricated as a TENG with a "sandwich" structure in single electrode mode. Moreover, the resulting TENG achieved electrical outputs with simple hand tapping and served as a self-powered device to light light-emitting diodes. This work displays a feasible strategy to build environment-tolerant and multifunctional organohydrogels, which possess potential applications in the wearable electronics and self-powered devices.
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Hydrogel-based flexible supercapacitors possess the merits of highly ionic conductivity and superior power density, but the existence of water limits their application in extreme temperature scenarios. Noticeably, it is a challenge for people to design more extremely temperature adaptable systems for flexible supercapacitors based on hydrogels with a wide temperature region. In this work, a wide-temperature flexible supercapacitor that can operate at -20-80 °C was fabricated by an organohydrogel electrolyte and its combined electrode (also known as an electrode/electrolyte composite). Upon introducing highly hydratable LiCl into an ethylene glycol (EG)/H2 O binary solvent, owing to the ionic hydration effect of LiCl and the hydrogen bond interaction between EG and H2 O molecules, the organohydrogel electrolyte exhibits satisfactory resistance to freezing (freezing point of -113.9 °C), anti-drying capability (78.2 % of weight retention after vacuum drying at 60 °C for 12â h) and excellent ionic conductivity both at room temperature (13.9â mS cm-1 ) and low temperature (6.5â mS cm-1 after 31â days at -20 °C). By using organohydrogel electrolyte as binder, the prepared electrode/electrolyte composite effectively reduces interface impedance and enhances specific capacitance due to the uninterrupted ion transport channels and extended interface contact area. The assembled supercapacitor delivers a specific capacitance of 149â F g-1 , a power density of 160â W kg-1 , and an energy density of 13.24â Wh kg-1 at a current density of 0.2â A g-1 . The initial 100 % capacitance can be maintained after 2000 cycles at 1.0â A g-1 . More importantly, the specific capacitances can be well maintained even at -20 and 80 °C. With other advantages such as excellent mechanical property, the supercapacitor is an ideal power source suitable for various working conditions.
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As flexible wearable devices, hydrogel sensors have attracted extensive attention in the field of soft electronics. However, the application or long-term stability of conventional hydrogels at extreme temperatures remains a challenge due to the presence of water. Antifreezing and antidrying ionic conductive organohydrogels were prepared using cellulose nanocrystals and gelatin as raw materials, and the hydrogels were prepared in a water/glycerol binary solvent by a one-pot method. The prepared hydrogels were characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. The mechanical properties, electrical conductivity, and sensing properties of the hydrogels were studied by means of a universal material testing machine and LCR digital bridge. The results show that the ionic conductive hydrogel exhibits high stretchability (elongation at break, 584.35%) and firmness (up to 0.16 MPa). As the binary solvent easily forms strong hydrogen bonds with water molecules, experiments show that the organohydrogels exhibit excellent freezing and drying (7 days). The organohydrogels maintain conductivity and stable sensitivity at a temperature range (-50 °C-50 °C) and after long-term storage (7 days). Moreover, the organohydrogel-based wearable sensors with a gauge factor of 6.47 (strain, 0-400%) could detect human motions. Therefore, multifunctional organohydrogel wearable sensors with antifreezing and antidrying properties have promising potential for human body monitoring under a broad range of environmental conditions.
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In recent years, gel-based ion conductor has been widely considered in wearable electronics because of the favorable flexibility and conductivity. However, it is of vital importance, yet rather challenging to adapt the gel for underwater and dry conditions. Herein, an anti-swelling and anti-drying, intrinsic conductor eutectogel is designed via a one-step radical polymerization of acrylic acid and 2, 2, 2trifluoroethyl methacrylate in binary deep eutectic solvents (DESs) medium. On the one hand, the synergistic effects of hydrophilic/hydrophobic heteronetworks can elicit the integrity stability of eutectogel in liquid environment. It is proved that both the mechanical property and conductivity are maintained after immersing in different salt, alkaline and acid solution and organic solvent for one month. On the other hand, the eutectogel inherits well conductivity (93 mS/m), anti-drying and antibacterial properties from DESs. Based on the above features, the resulting eutectogel can be assembled as smart sensor for stable information transmission in air and underwater with fast response time (1 s), high sensitivity (Gauge factor = 1.991) and long-time reproducibility (500 cycles, 70 % strain). Considering the simple preparation and integration of multiple functions, the binary cooperative complementary principle can provide insights into the development of next-generation conductive soft materials.
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Conductive hydrogels with high electrical conductivity, ductility, and anti-dryness have promising applications in flexible wearable electronics. However, its potential applications in such a developing field are severely hampered by its extremely poor adaptability to cold or hot environmental conditions. In this research, an "organic solvent/water" composite conductive hydrogel is developed by introducing a binary organic solvent of EG/H2O into the system using a simple one-pot free radical polymerization method to create Ti3C2TX MXene nanosheet-reinforced polyvinyl alcohol/polyacrylamide covalently networked nanocomposite hydrogels (PAEM) with excellent flexibility and mechanical properties. The optimized PAEM contains 0.3 wt% MXene has excellent mechanical performance (tensile elongation of ~1033%) and an improved modulus of elasticity (0.14 MPa), a stable temperature tolerance from -50 to 40 °C, and a high gauge factor of 10.95 with a long storage period and response time of 110 ms. Additionally, it is worth noting that the elongation at break at -40 °C was maintained at around 50% of room temperature. This research will contribute to the development of flexible sensors for human-computer interaction, electronic skin, and human health monitoring.
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Hydrogels are often used to fabricate strain sensors; however, they also suffer from freezing at low temperatures and become dry during long-time storage. Encapsulation of hydrogels with elastomers is one of the methods to solve these problems although the adhesion between hydrogels and elastomers is usually low. In this work, using bovine serum protein (BSA) as the natural globulin model and glycerol/H2O as the mixture solvent, BSA/polyacrylamide organohydrogels (BSA/PAAm OHGs) were prepared by a facile photopolymerization approach. At the optimal condition, BSA/PAAm OHG demonstrated not only high toughness but also tough adhesion properties, which could strongly adhere to various substrates, such as glass, metals, rigid polymeric materials (even poly(tetrafluoroethylene), i.e., PTFE), and soft elastomers. Moreover, BSA/PAAm OHG was flexible and showed tough adhesion at -20 °C. The toughening mechanism and the adhesive mechanism were proposed. On being encapsulated by poly(dimethylsiloxane) (PDMS), it illustrated good antidrying performance. After introducing a conductive filler, the encapsulated BSA/PAAm OHG could be used as a strain sensor to detect human motions. This work provides a better understanding of the adhesive mechanism of natural protein-based organohydrogels.
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Adhesivos , Globulinas , Adhesivos/química , Elastómeros , Conductividad Eléctrica , Humanos , Hidrogeles/químicaRESUMEN
Through a simple strategy of immersion in a mixed solution of water/ethylene glycol (EG)/lithium chloride (LiCl), self-healing carboxymethyl chitosan (CA) hydrogels, that is, CA/N-vinylpyrrolidone-EG-Li+ hydrogels (CEH) with an ultra-low-temperature freezing resistance below -70 °C were fabricated. The introduction of electrolyte ions and small-molecule polyol also made these hydrogels highly conductive (0.8 S m-1) and imparted antidrying property to them, showing stable and reversible sensitivity to finger-wrist bending as well as 150 cycles of stretching. Such hydrogels also presented highly efficient self-healing ability, with a stress-strain healing efficiency of over 90%. Furthermore, the CEH-based sensors maintained a stable sensing performance over a wide range of temperatures below the freezing point (from -10 to -70 °C) and exhibited stable sensitivity to temperatures with fast response and no significant hysteresis. The present work is expected to provide a simple and sustainable route for the preparation of multifunctional antifreezing conductive hydrogels based on CA, leading to a wide range of potential applications in soft sensor devices.
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Quitosano , Hidrogeles , Conductividad Eléctrica , Iones , AguaRESUMEN
The rapid development of flexible electronic devices has caused a boom in researching flexible sensors based on hydrogels, but most of the flexible sensors can only work at room temperature, and they are difficult to adapt to extremely cold or dry environments. Here, the flexible hydrogel fibers (PEDOT:PSS@PVA) with excellent resistance to extreme environments have been prepared by adding glycerin (GL) to the mixture of poly(vinyl alcohol) (PVA) and poly 3,4-dioxyethylene thiophene:polystyrene sulfonic acid (PEDOT:PSS) because GL molecules can form dynamic hydrogen bonds with an elastic matrix of PVA molecules. It is found that the prepared sensor exhibits very good flexibility and mechanical strength, and the ultimate tensile strength can reach up to 13.76 MPa when the elongation at break is 519.9%. Furthermore, the hydrogel fibers possess excellent water retention performance and low-temperature resistance. After being placed in the atmospheric environment for 1 year, the sensor still shows good flexibility. At a low temperature of -60 °C, the sensor can stably endure 1000 repeated stretches and shrinks (10% elongation). In addition to the response to a large strain, this fiber sensor can also detect extremely small strains as low as 0.01%. It is proved that complex human movements such as knuckle bending, vocalization, pulse, and others can be monitored perfectly by this fiber sensor. The above results mean that the PEDOT:PSS@PVA fiber sensor has great application prospects in physiological monitoring.
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Compuestos Bicíclicos Heterocíclicos con Puentes , Hidrogeles , Compuestos Bicíclicos Heterocíclicos con Puentes/química , Ambientes Extremos , Glicerol/química , Humanos , Hidrogeles/química , Monitoreo Fisiológico , PolímerosRESUMEN
Using solid polymer electrolytes has been proven to be an efficient strategy to address the metal dendrites and pursuing high-voltage performance. Polyethylene oxide (PEO), as a popular polymer matrix, hardly works for zinc ion batteries due to its poor zinc ionic conductivity and the poor interfacial adhesion. Here, an ionic liquid, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([Emim]OTF), was applied as a plasticizer to tune the room-temperature ionic conductivity and mechanical properties of PEO membrane electrolyte. Additional nanofillers ZnO were utilized to enhance the plasticity and modulus. With an optimized composition, the membrane exhibits a high modulus and soft mechanics, which can facilitate the reversible stripping/plating of Zn without formation of Zn dendrites. The optimized polymer electrolyte achieved an ionic conductivity of 2.3 × 10-3 S cm-1 at room temperature with a softness of 5.1 mm. By applying the resulted soft membrane electrolyte for a Zn-MnO2 battery, a capacity of 137 mAh g-1 is achieved at 30 mA g-1 even without the contribution from H+. Such an electrolyte also works for Prussian blue analogue cathodes. Importantly, the addition of [Emim]OTF can enhance the soft contact with the electrodes, and a stable output is delivered under severe deformations for the assembled flexible devices.
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[This corrects the article DOI: 10.3389/fbioe.2022.837750.].
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Conductive hydrogels have potential applications in shielding electromagnetic (EM) radiation interference in deformable and wearable electronic devices, but usually suffer from poor environmental stability and stretching-induced shielding performance degradation. Although organohydrogels can improve the environmental stability of materials, their development is at the expense of reducing electrical conductivity and thus weakening EM interference shielding ability. Here, a MXene organohydrogel is prepared which is composed of MXene network for electron conduction, binary solvent channels for ion conduction, and abundant solvent-polymer-MXene interfaces for EM wave scattering. This organohydrogel possesses excellent anti-drying ability, low-temperature tolerance, stretchability, shape adaptability, adhesion and rapid self-healing ability. Two effective strategies have been proposed to solve the problems of current organohydrogel shielding materials. By reasonably controlling the MXene content and the glycerol-water ratio in the gel, MXene organohydrogel can exhibit exceptionally enhanced EM interference shielding performances compared to MXene hydrogel due to the increased physical cross-linking density of the gel. Moreover, MXene organohydrogel shows attractive stretching-enhanced interference effectiveness, caused by the connection and parallel arrangement of MXene nanosheets. This well-designed MXene organohydrogel has potential applications in shielding EM interference in deformable and wearable electronic devices.
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Conductive hydrogel is a vital candidate for the fabrication of flexible and wearable electric sensors due to its good designability and biocompatibility. These well-designed conductive hydrogel-based flexible strain sensors show great potential in human motion monitoring, artificial skin, brain computer interface (BCI), and so on. However, easy drying and freezing of conductive hydrogels with high water content greatly limited their further application. Herein, we proposed a natural polymer-based conductive hydrogel with excellent mechanical property, low water loss, and freeze-tolerance. The main hydrogel network was formed by the Schiff base reaction between the hydrazide-grafted hyaluronic acid and the oxidized chitosan, and the added KCl worked as the conductive filler. The reversible crosslinking in the prepared hydrogel resulted in its resilience and self-healing feature. At the same time, the synthetic effect of KCl and glycerol endowed our hydrogel with outstanding anti-freezing property, while glycerol also endowed this hydrogel with anti-drying property. When this hydrogel was assembled as a flexible strain sensor, it showed good sensitivity (GF = 2.64), durability, and stability even under cold condition (-37°C).
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With the rising demand for wearable, multifunctional, and flexible electronics, plenty of efforts aiming at wearable devices have been devoted to designing sensors with greater efficiency, wide environment tolerance, and good sustainability. Herein, a thin film of double-network ionic hydrogel with a solution replacement treatment method is fabricated, which not only possesses excellent stretchability (>1100%) and good transparency (>80%), but also maintains a wide application temperature range (-10~40 °C). Moreover, the hydrogel membrane further acts as both the flexible electrode and a triboelectric layer, with a larger friction area achieved through a micro-structure pattern method. Combining this with a corona-charged fluorinated ethylene propylene (FEP) film, an electret/hydrogel-based tactile sensor (EHTS) is designed and fabricated. The output performance of the EHTS is effectively boosted by 156.3% through the hybrid of triboelectric and electrostatic effects, which achieves the open-circuit peak voltage of 12.5 V, short-circuit current of 0.5 µA, and considerable power of 4.3 µW respectively, with a mentionable size of 10 mm × 10 mm × 0.9 mm. The EHTS also demonstrates a stable output characteristic within a wide range of temperature tolerance from -10 to approximately 40 °C and can be further integrated into a mask for human breath monitoring, which could provide for a reliable healthcare service during the COVID-19 pandemic. In general, the EHTS shows excellent potential in the fields of healthcare devices and wearable electronics.
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Hydrogels with mechanical elasticity and conductivity are ideal materials in wearable devices. However, traditional hydrogels are fragile upon mechanical loading and lose functions in climate change because the internal water undergoes freeze and dehydration. Herein, we synthesize stable emulsions at high and low temperatures by introducing glycerol into the W/W emulsions. Then the high-stable emulsions are used as templates to produce the freestanding emulsion gels with enhanced mechanical strength and conductivity. The introduction of glycerol endows emulsions and emulsion gels with high and low temperature resistance (-20 to 90 °C). The fabricated strain sensors based on emulsion gels show high sensitivity (gauge factor=6.240), high stretchability (1081 %), fatigue resistance, self-healing and adhesion properties, realizing the repeatable and accurate detection of various human motions. These high-performance and eco-friendly emulsion gels can be promising candidates for next-generation artificial skin and human-machine interface.
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Hidrogeles , Dispositivos Electrónicos Vestibles , Conductividad Eléctrica , Emulsiones , Geles , Humanos , TemperaturaRESUMEN
Conductive hydrogels can be used in wearable electronics integrated with skin, but the bulk structure of existing hydrogel-based temperature sensors limits the wearing comfort, response/recovery speeds, and sensitivity. Here, stretchable and transparent temperature sensors based on a novel thin-film sandwich structure (TFSS) are designed, which display unprecedented thermal sensitivity (24.54%/°C), fast response time (0.19 s) and recovery time (0.08 s), a broad detection range (from -28 to 95.3 °C), high resolution (0.8 °C), and high stability. The thin hydrogel layer (12.15 µm) is encapsulated by two thin elastomer layers, which prevent the water evaporation and enhance the heat transfer, leading to the boosted stability and accelerated response/recovery speeds. The nondrying and antifreezing capabilities are further promoted by the hydratable lithium bromide (LiBr) incorporated in the hydrogel, enabling it to avoid dehydration in an extremely arid environment and freeze below subzero temperatures (freezing point below -120 °C). A comparative study reveals that the thermal sensitivity displayed by the TFSS sensor in capacitance mode is several times higher than that in conventional conductance/resistance mode above room temperature. Importantly, a new mechanism based on a horizontal plate capacitance model is proposed to understand the high sensitivity by considering the permittivity and geometry variations of TFSS. The thin TFSS, stretchability and transparency enable the sensor to be conformally and comfortably attached to human skin for real-time and reliable monitoring of various human motions, physical states, skin temperature, etc., without affecting the appearance.
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Hidrogeles , Temperatura , Dispositivos Electrónicos Vestibles , Técnicas Biosensibles/métodos , Elastómeros , Conductividad Eléctrica , HumanosRESUMEN
Hydrogels are attractive, active materials for various e-skin devices based on their unique functionalities such as flexibility and biocompatibility. Still, e-skin devices are generally limited to simple structures, and the realization of optimal-shaped 3D e-skin devices for target applications is an intriguing issue of interest. Furthermore, hydrogels intrinsically suffer from drying and freezing issues in operational capability for practical applications. Herein, 3D artificial skin devices are demonstrated with highly improved device stability. The devices are fabricated in a target-oriented 3D structure by extrusion-based 3D printing, spontaneously heal mechanical damage, and enable stable device operation over time and under freezing conditions. Based on the material design to improve drying and freezing resistance, an organohydrogel, prepared by solvent displacement of hydrogel with ethylene glycol for 3 h, exhibits excellent drying resistance over 1000 h and improved freezing resistance by showing no phase transition down to -60 °C while maintaining its self-healing functionality. Based on the improved drying and freezing resistance, artificial skin devices in target-oriented optimal 3D structures are presented, which enable accurate positioning of touchpoints even on a complicated 3D structure stably over time and excellent operation at temperatures below 0 °C without losing their flexibility.
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Piel Artificial , Conductividad Eléctrica , Congelación , Hidrogeles , TactoRESUMEN
Fiber and textile electronics provide a focus for a new generation of wearable electronics due to their unique lightness and flexibility. However, fabricating knittable fibers from conductive materials with high tensile and transparent properties remains a challenge, especially for applicability in harsh environments. Here, we report a simple photopolymerization approach for the rapid preparation of a new type of a transparent conductive polymer fiber, poly(polymerizable deep eutectic solvent (PDES)) fiber, which exhibits excellent stability at high/low temperature, in organic solvents, especially in dry environments, and overcomes the volatility and freezability of traditional gel materials. A poly(PDES) fiber possesses outstanding mechanical and sensing properties, including negligible hysteresis and creep, fast resilience after a long stretch (10 min), and signal stability during high-frequency cyclic stretching (1 Hz, 10â¯000 cycles). In addition, the poly(PDES) fibers are knitted into a plain-structured sensor on textile with breathability and high tolerance to damage, enabling stable and accurate monitoring of human stretching, bending, and rotation motions. Furthermore, its dry-cleaning resistance guarantees the feasibility of long-term monitoring, with the electrical signal remaining stable after five dry-cleaning cycles. These promising features of poly(PDES) fibers will promote potential applications in the fields of human movement monitoring, intelligent fibers, and soft robotics.