抗冻水凝胶的制备及其在柔性电子领域的应用

水凝胶具有优异的柔韧性、离子运输性和可调的机械性,在柔性电子领域具有广阔的应用前景。然而,水凝胶电子器件在严寒气候下容易冻结失效,严重限制了其在低温环境下的应用潜力。向水凝胶中引入低温防护剂可以赋予水凝胶抗冻性能,拓宽水凝胶电子器件的工作温度。该文从溶质离子、离子液体、有机溶剂以及抗冻蛋白改性水凝胶4个方面,综述了近年来抗冻水凝胶的制备方法和抗冻机理;阐述了抗冻水凝胶在超级电容器、传感器和电池等柔性电子领域的应用进展;归纳了抗冻水凝胶电子材料面临的问题与挑战,并展望了抗冻水凝胶电子材料的发展趋势;最后指出以天然可再生资源为原料开发具有优异机械性能、电化学性能、生物无毒性、生物相容性和生物可降解的抗冻水凝胶成为下一步研究重点,同时设计优化柔性电子装置、提高器件安全可靠性和输出稳定性也将成为重要的研究方向之一。抗冻水凝胶的制备及其应用研究将促进柔性电子功能材料领域的快速发展。     

导电水凝胶的制备及应用研究进展

导电水凝胶是一类将亲水性基质和导电介质有机结合的新型水凝胶,具有较高的柔韧性、可调的力学性能和优异的电化学性能,在柔性电子设备等领域具有广阔的应用前景。本文综述了导电水凝胶材料的研究前沿和动态,介绍了导电水凝胶的分类及制备方法,讨论了导电水凝胶的结构设计与性能,重点阐述了导电水凝胶材料的应用研究进展,归纳了导电水凝胶材料面临的问题与挑战,并展望了导电水凝胶材料的发展趋势,指出采用天然可再生资源为原料开发具有高导电性、力学性能稳定、耐极端温度、生物相容性和生物可降解的导电水凝胶将成为下一步研究重点,同时优化柔性电子装置、提高器件输出稳定性也将成为重要的研究方向之一。导电水凝胶的制备及应用研究将促进柔性电子功能材料领域的快速发展。     

纳米纤维素纤维凝胶特性及其应用

纳米纤维素纤维在水溶液中可以通过物理缠绕以及氢键结合的方式形成具有稳定三维网络结构的水凝胶。纳米纤维素水凝胶具有无毒性及良好的生物相容性,在生命科学领域应用前景广阔。而纳米纤维素气凝胶保持凝胶的三维网络结构,其高比表面积、低密度及优异的隔热性能等在建筑、能源电子器件、油水分离等领域也同样有着巨大的应用潜力。本文从纳米纤维素基本特性、纳米纤维素水凝胶、纳米纤维气凝胶研究及应用情况进行了介绍,并分别对纳米纤维素水凝胶与气凝胶的优异性能及应用进展进行了总结。     

双金属离子交联海藻基抗冻水凝胶的制备

以海藻酸钠为主要材料,依次通过Ca2+和Zn2+离子交联,制备了双金属离子交联海藻基水凝胶.研究了水凝胶制备条件对其压缩强度、拉伸强度、抗冻性以及电化学阻抗的影响,合成的水凝胶具有较好的抗压缩性能和抗拉伸性能.当在浓度为1.25 g/mL 的ZnCl2溶液中交联72 h时,钙锌双交联海藻基水凝胶在25℃和-18℃的压缩...     

抗菌粘附型酪蛋白基纳米复合水凝胶的制备

近年来，水凝胶因其独特的网络结构和功能性受到了生物医药、食品环保等领域的广泛关注，其中以生物质材料为基体的绿色功能化水凝胶成为了重要研究方向。本研究以酪蛋白为基体，引入纳米氧化锌（ZnO NPs），通过“半溶解溶胶-凝胶酸化法”制备抗菌粘附型酪蛋白基纳米复合水凝胶。实验结果表明：所制备的纳米复合水凝胶具有立体的三维网络结构，孔径分布均一；当引入ZnO NPs用量为酪蛋白的3%时，其溶胀率可达79.19%；抗张强度和断裂伸长率分别可达1.9 MPa和137.4%；该水凝胶对于皮肤、玻璃、塑料、金属等多种材料表现出了优异的粘附性；且对大肠杆菌与金黄色葡萄球菌均具有良好的抗菌性能，在生物敷料领域展现出较好的应用前景。     

基于液态金属的水凝胶应变传感器

近年来，基于导电水凝胶的应变传感器发展迅速，液态金属作为一种新型导电材料由于具有高导电性、良好的生物相容性、柔性和可变性，在导电水凝胶传感器的制备和应用中受到了越来越多的关注。本文介绍了液态金属以分散的液滴和连续的流体两种形式在导电水凝胶制备中的应用，及所制备的基于液态金属导电水凝胶传感器的性能，最后，对基于液态金属的水凝胶传感器的应用前景进行了展望。     

高分子水凝胶材料在生物医药领域的应用

水凝胶属于典型三维网络材料,主要是由高分子聚合物构成。天然高聚物以及相关衍生材料制备的水凝胶具有生物可降解性、相容性、对环境无污染等特点,在生物医药领域获得了颇为广泛的运用。文章综述了高分子水凝胶制备的方法,介绍了其在生物医药领域的相关应用,以期为其在医学领域的开发和研究提供相应的参考。     

自愈合凝胶在柔性传感器中的应用研究进展

自愈合凝胶具有优异的机械性能、良好的生物相容性和延长材料使用寿命功能等特性,已广泛应用在电子皮肤、柔性机器人、可穿戴设备等方面。凝胶基质结构的可调性和导电材料选择的多样性也为制备具有不同功能的柔性传感器提供了可能。该文根据交联方式、功能性类型、愈合方式和胶凝剂相对分子质量大小4种分类方式将自愈合凝胶进行了分类,并详细介绍了各种自愈合凝胶的成胶机制和性能特点。综述了自愈合凝胶在柔性传感器中力学、光电和生物方面的国内外研究现状。最后,讨论了该研究领域仍存在的问题,并对其未来发展前景及方向进行了简要展望。     

磁性水凝胶的制备及其应用研究进展

近些年来，磁性水凝胶材料因其优异的磁性、稳定性和良好的生物相容性而备受关注。同时，对磁性水凝胶的材料改性工作也在不断推进，以提高磁性水凝胶材料的吸附、运载等特定能力。介绍了磁性水凝胶材料的制备，包括共混法、接枝法、原位沉淀法和溶胀法。重点介绍了其在重金属离子吸附、药物运输、癌症治疗等领域的应用。考虑到对未来发展的贡献，对磁性水凝胶在智能多功能材料方面的应用进行了展望。     

谷氨酸/N-琥珀酰化壳聚糖水凝胶的制备和性能

以琥珀酸酐、壳聚糖为原料制备水溶性的N-琥珀酰化壳聚糖(NSC),再以谷氨酸(GA)为交联剂,在室温条件下,一定质量的GA和NSC在水溶液中通过自组装制备了GA/NSC水凝胶,研究了GA/NSC水凝胶的稳定性和溶胀性能,运用红外光谱(IR)、差示扫描量热仪(DSC)、扫描电子镜(SEM)等对其结构进行了表征,并考察了GA/NSC水凝胶的细胞毒性。结果表明,GA/NSC水凝胶为pH响应的离子交联水凝胶,具有较好的溶胀性能及生物相容性。     

Janus POSS-based hydrogel electrolytes with highly stretchable and low-temperature resistant performances for all-in-one supercapacitors

Conductive hydrogels can be utilized in the field of flexible supercapacitors due to their stretchable properties and high ionic conductivity. However, many of the conductive hydrogels lose their stretchability and conductivity at subzero temperatures. Herein, a novel Janus POSS-based hydrogel electrolyte that shows excellent flexibility and ionic conductivity at low temperatures is designed and prepared by the copolymerization of acrylamide and a water-soluble Janus-type polyhedral oligomeric silsesquioxane (AS-POSS) containing sodium sulfonate groups and double bonding groups. The sodium sulfonate groups of AS-POSS and LiCl endow the hydrogel electrolyte with excellent anti-freezing ability. Simultaneously, the double bonding groups of AS-POSS enable a successful POSS crosslinking in the polymer network, resulting in a highly stretchable hydrogel electrolyte (1445%) with high ionic conductivity (0.067 S cm⁻¹) at −20°C. Thereafter, the all-in-one flexible supercapacitor is prepared by in-situ polymerization of aniline. Based on the exceptional anti-freezing properties of the Janus POSS-based hydrogel electrolyte, the all-in-one supercapacitor exhibits stable electrochemical performance (>90% capacitance retained under deformation at −20°C) and excellent cycling stability (only 19.7% capacitance decay over 2000 charge/discharge cycles at −20°C) at low temperatures. The Janus POSS-based hydrogel electrolyte is expected to be a promising gel electrolyte for an all-in-one supercapacitor that resists freezing.     

Superfast Self‐Healing and Photothermal Active Hydrogel with Nondefective Graphene as Effective Additive

2D graphene with high quality holds great promise in improving the performance of the hydrogels owing to its exceptional electronic, thermal, and mechanical properties. However, the structure defects existed in graphene restrict its further applications. Herein, a simple and green method of fabricating defect‐free graphene nanosheets with the assistance of supercritical carbon dioxide (SC CO₂) is designed. The graphene nanosheets directly assemble with acrylic acid monomer and clay, and a flexible semitransparent hydrogel is fabricated. Benefiting from the excellent properties of the defect‐free graphene, the hydrogel exhibits the high mechanical performance, superfast self‐healing capability, excellent conductivity, and super photothermal conversion efficiency. According to the advantages above, the graphene/poly(acrylic acid)/clay hydrogels can be used for intelligent sensors for disease diagnosis, artificial electronic skin, and military stealth materials in the near future.     

Tough and recoverable triple‐network hydrogels based on multiple pairs of toughing mechanisms with excellent ionic conductivity as stable strain sensors

The emerging applications of hydrogels in flexible devices require it possess multifunctional properties including stable mechanical and functions under various deformations or external environments. Herein, a multifunctional polyvinyl alcohol/M‐alginate/PAM hydrogel with very excellent mechanical properties and sensing functions was fabricated by introducing multiple pairs of toughing mechanisms into triple network (TN). The multiple supramolecular physical networks work as sacrificial networks to toughen the materials when hydrogel deforms. The broken bonds can reform upon unloading endowing the recovery of hydrogels' properties and functions with the assistance of the elastic covalent network. The optimal TN hydrogels are extremely tough (a fracture strength of 512 kPa, a fracture toughness of 3 MJ/m³) and recoverable from fatigue damage (~77% toughness recovery after 5 min resting at room temperature). The presence of abundant ionic species endows the tough and recoverable TN hydrogels high ionic conductivity and high sensitivity as strain sensors. Moreover, such TN hydrogels with multi‐bond crosslinking in three networks can potentially guarantee stable mechanical and sensor functions under various deformations or external environments compared to the DN candidates. This work provides a simple strategy for fabricating multifunctional hydrogels with high stability to fulfill its flexible devices applications. POLYM. ENG. SCI., 59:1657–1666 2019. © 2019 Society of Plastics Engineers     

The composite hydrogel with “2D flexible crosslinking point” of reduced graphene oxide for strain sensor

Intelligent hydrogels with excellent flexibility, biocompatibility, and stimulus responsivity can mimic the functions of the skin to detect human motions. However, the low mechanical strength limits its application in the field of biomimetic materials. In this work, polyacrylamide-reduced graphene oxide (PAM-rGO) composite hydrogels were prepared by the combination of PAM and partially rGO, and their biomimetic strain sensors were studied. The rGO played the role of “2D flexible crosslinking point” in the composite hydrogel. Through the H-bonds between rGO and hydrogels, the toughness and strength of the composite hydrogel were enhanced. The maximum strain of the hydrogel changed from 751% to 1097%, and the maximum stress changed from 0.065 to 0.20 MPa. On the other hand, the interaction between the PAM backbone and the rGO provided a credible resistance response to the stimulation of strain. The better linear relationship between resistance and length was built, with R² of 0.992. Furthermore, the composite hydrogels were assembled into wearable devices to monitor human-motion, including fingers bending, elbows bending and walking. The experimental results showed that the PAM-rGO composite hydrogel had great potential in the field of bionic skin.     

面向柔性超级电容器的功能水凝胶材料的研究进展

功能水凝胶作为一种三维高分子网络结构的软湿材料,具有可灵活调控的功能特性,为设计和构建高性能柔性超级电容器提供了理想的材料。本文综述了近年来面向柔性超级电容器领域的功能水凝胶材料的研究进展,重点分类介绍了面向电化学双层电容器和赝电容器的功能水凝胶材料的设计构建和性能强化。探讨了通过水凝胶电解质及电极材料的组成结构设计和性能调控来提升超级电容器的电化学性能和力学性能的策略。同时,探讨了水凝胶电解质及电极材料的组成结构设计和性能调控在实现其自愈合、高耐寒等多样化功能特性方面的重要作用。最后,对功能水凝胶材料柔性超级电容器在高储能、高柔性、高保水、自愈合、高耐寒、绿色可降解等方面的未来发展进行了展望。     

Polyaniline/Poly(acrylamide‐co‐sodium acrylate) Porous Conductive Hydrogels with High Stretchability by Freeze‐Thaw‐Shrink Treatment for Flexible Electrodes

With the development of alternatives to traditional fossil energy and the rise of wearable technology, flexible energy storage devices have attracted great attention. In this paper, a polyaniline/poly(acrylamide‐sodium acrylate copolymer) hydrogel (PASH) with high flexibility and excellent electrochemical properties for flexible electrodes is fabricated by freeze‐thaw‐shrink treatment of a highly water‐absorptive hydrogel, together with in‐situ polymerization of aniline at a low aniline concentration (0.1 mol L^?1). The PASH exhibits a conductivity of 4.05 S m^?1 and an elongation at break of 1245%. The freeze‐thaw‐shrink treatment greatly improves the electrochemical performance and stability of the conductive PASH. The area specific capacitance of PASH reaches 849 mF cm^?2 and the capacitance maintains 89% after 1000 galvanostatic charge–discharge cycles. All the raw materials are conventional industrialized materials and no additional templating agent is needed during the entire synthesis process. This study provides a cost‐efficient approach for the fabrication of conductive polymer hydrogels, which has a broad application prospect in flexible energy storage electronic devices.     

Highly Stretchable,Transparent, and Bio‐Friendly Strain Sensor Based on Self‐Recovery Ionic‐Covalent Hydrogels for Human Motion Monitoring

Stretchable, flexible, and strain‐sensitive hydrogels have gained tremendous attention due to their potential application in health monitoring devices and artificial intelligence. Nevertheless, it is still a huge challenge to develop an integrated strain sensor with excellent mechanical properties, broad sensing range, high transparency, biocompatibility, and self‐recovery. Herein, a simple paradigm of stretchable strain sensor based on multifunctional hydrogels is prepared by constructing synergistic effects among polyacrylamide (PAM), biocompatible macromolecule sodium alginate (SA), and Ca ion in covalently and ionically crosslinked networks. Under large deformation, the dynamic SA‐Ca²⁺ bonds effectively dissipate energy, serving as sacrificial bonds, while the PAM chains bridge the crack and stabilize the network, endowing hydrogels with outstanding mechanical performances, for instance, high stretchability and compressibility, as well as excellent self‐recovery performance. The hydrogel is assembled to be a transparent and wearable strain sensor, which has good sensitivity and very wide sensing range (0–1700%), and can precisely detect dynamic strains, including both low and high strains (20–800% strain). It also exhibits fast response time (800 ms) and long‐time stability (200 cycles). The sensor can monitor and distinguish complicated human motions, opening up a new route for broad potential applications of eco‐friendly flexible strain‐sensing devices.     

Highly Stretchable,Tough, and Conductive Ag@Cu Nanocomposite Hydrogels for Flexible Wearable Sensors and Bionic Electronic Skins

Flexible conductive materials and flexible electronic devices are driving the development of the next generation of cutting-edge wearable electronics. However, the existing hydrogel-based flexible conductive materials have limited tensile capacity, low toughness, and poor anti-fatigue performance, resulting in narrow sensing area and insufficient durability. In this paper, a conductive nanocomposite hydrogel with high ductility, toughness, and fatigue resistance is prepared by combining silver coated copper (Ag@Cu) nanoparticles with gelatin followed by one-step immersion in sodium sulfate (Na₂SO₄) solution. The salting-out of gelatin in Na₂SO₄ solution greatly improve the mechanical properties of this gelatin-based hydrogel. The uniform distribution of Ag@Cu nanoparticles inside the whole hydrogel endow the composite hydrogel with excellent electrical conductivity (1.35 S m⁻¹). In addition, it displayed high and stable tensile strain sensitivity over a wide strain range (gauge factor = 2.08). Therefore, the Ag@Cu-Gel hydrogel is sensitive and stable enough to be successfully utilized as flexible wearable sensor for detecting human motion signals in real time, such as bending of human joints, swallowing, and throat vocalization. Furthermore, this hydrogel is also suitable for application as electronic skin for bionic robots. The above results demonstrate the promising application of Ag@Cu-Gel hydrogel for wearable electronics.     

Conductive double-network hydrogel for a highly conductive anti-fatigue flexible sensor

Improving the mechanical properties of hydrogels is a prime example of their large-scale, diverse applications. Herein, we report a one-pot method for preparing a double network system hydrogel where the polyvinyl alcohol served as the first polymer backbone, acrylamide as the second network, and N, N′-Methylenebisacrylamide as the cross-linker, and the prepared hydrogels presented excellent mechanical properties with 1168% tensile strain and 598 kPa compressive strength. Through the metal–ligand bonds, an electrolyte solution containing Cu²⁺ was introduced into the hydrogel, which exhibits higher water retention than other electrolyte-containing hydrogels. Specially, the hydrogel was able to retain water for 8 h under extreme dry conditions at 60°C. The GF value was calculated to be 0.124 when the strain was 0%–64.2%. Furthermore, the hydrogel flexible sensor can detect changes in ambient temperature. When the ambient temperature rises, its relative resistance also tends to rise. In conclusion, this hydrogel sensor offers great potential applications in flexible sensors.