高分子导电水凝胶的制备及在柔性可穿戴电子设备中的应用

水凝胶是具有高含水量、可变形性和良好生物相容性的材料,其中导电水凝胶具有良好的导电性、可调节的机械性及自黏附性等特征,逐渐成为制备柔性可穿戴电子设备的最佳候选材料。近年来,具有生物相容性、机械柔韧性和抗疲劳性的导电水凝胶得到广泛研究,能够实现多种生理信号和物理信号的监测及传输,促进了柔性可穿戴电子设备的发展。柔性可穿戴电子设备逐渐成为人机交互技术和人工智能领域的主要研究方向。导电水凝胶通过使用导电聚合物、导电填料、自由离子及其混合物来合成,根据导电机理,所制备的导电水凝胶可分为电子导电水凝胶、离子导电水凝胶和混合电子-离子导电水凝胶。本文讨论了导电水凝胶的制备方法,总结了导电水凝胶在可拉伸性、导电性、生物相容性和自修复性等功能方面的研究进展及其在柔性可穿戴电子设备中的应用,期望导电水凝胶可以取得更好的发展。     

杂化交联网络水凝胶的制备及表皮传感性能

以丙烯酰胺（AAm）单体和甲基丙烯酰氧乙基三甲基氯化铵（DMC）阳离子单体为共聚单体,添加一定量阴离子聚电解质聚丙烯酸钠（PAAS）,制备具有杂化交联网络的离子导电水凝胶P(AAm-DMC)-PAAS。采用万能试验机和电化学工作站对其力学性能和应变敏感性能进行测试。结果表明,水凝胶最大应力可达（88.4±4.7） kPa,最大应变为（1 030.8±71.7）%。由于PAAS和DMC能电离出丰富的游离离子,水凝胶无需额外添加导电填料即可保持较高的离子电导率（0.684 S/m）和应变变化的快速响应,灵敏因子约为2.409(0～70%应变范围内)。制备的水凝胶可作为可穿戴应变传感器监测人体运动,还可以组装成表皮电极对人体电生理信号进行准确检测。     

导电水凝胶基柔性电子传感系统——柔性电子创新实验设计

导电水凝胶兼具生物医用材料和导电材料特征,可应用于医疗康复、运动监测和人机交互等领域。为提高柔性电子学专业本科生的创新意识与实验技能,本实验设计了一种纳米凝胶材料交联的导电水凝胶,通过探索加聚型水凝胶聚合过程中引发剂浓度和交联机制,阐明材料结构组分对水凝胶基柔性电子器件使用耐久性能及传感性能的影响。通过创新实验设计,柔性电子学专业本科生可以学习到高分子乳液聚合、水凝胶制备以及应力应变传感性能表征等知识点,深入理解交联剂结构设计对材料功能性的影响。此外,本实验还设计了基于水凝胶柔性电子传感器的可穿戴传感系统,通过集成可控制小车移动的智能手套,以及用于控制电脑游戏的水凝胶控制器,将前沿科研与本科实验教学任务紧密结合,有利于激发柔性电子、材料、电子信息等专业本科生对于科研的兴趣和创新探索的科研精神。     

高强度银纳米线/聚丙烯酰胺复合水凝胶的制备及导电性能研究

近年来,导电水凝胶作为一种功能聚合物软材料在柔性电子器件领域显示出广泛的应用前景,因此发展高强度导电水凝胶的合成方法在基础和应用研究中均具有重要的价值.本文提出了一种制备高强度导电水凝胶的简便方法,利用银-硫配位作用实现一维银纳米线(AgNWs)与含硫有机聚合物的有效复合,在提高水凝胶强度的同时,赋予其高的导电性.具体制备步骤如下:首先通过1-烯丙氧基-2,3-环硫丙烷的开环聚合得到侧基带乙烯基的线性聚硫醚(P1),通过巯-烯click反应引入足够量的羧基,赋予其水溶性.修饰后的线性聚硫醚(P2)与一维AgNWs通过银-硫配位作用制备复合交联剂(AgNWs@P2).该交联剂与丙烯酰胺(Am)单体以过硫酸钾(KPS)为引发剂,在水溶液中进行自由基聚合制备银纳米线/聚丙烯酰胺复合水凝胶(AgNWs/PAm composite hydrogel, AC gel).高分辨场发射扫描电子显微镜的测试证实,AgNWs与P2在水凝胶中实现了纳米尺寸上的复合.刚性AgNWs的引入赋予水凝胶优异的力学强度,其拉伸应变和断裂强度可达到～4500%和～2.2 MPa.该水凝胶具有高导电性(σ=0.44 S/...     

Hofmeister效应辅助的蛋白质基水凝胶应变传感器

以酪蛋白酸钠和明胶为原料, 通过简单的在硫酸铵溶液中浸泡的方法, 借助Hofmeister效应制备了一种强韧导电的酪蛋白酸钠/明胶水凝胶, 克服了蛋白质基水凝胶柔软、 易碎的问题. 测试结果表明, 该水凝胶具有优异的机械性能, 最大拉伸应力为3.55 MPa, 最大拉伸应变为1375%; 水凝胶的最大电导率为0.0954 S/cm, 导电灵敏因子为0.53. 用该水凝胶制备的传感器对不同大小及不同速率的应变均具有分辨能力, 能够监测人体不同部位的运动, 且传感器的信号传输具有稳定性和准确性, 表明该水凝胶是监测人体健康和运动的理想材料. 该水凝胶还具有良好的形状记忆性能. 这一策略为制备全天然蛋白质基水凝胶开辟了新的思路, 扩展了水凝胶在生物医学和电子传感等相关领域的应用前景.     

基于仿生MXene纤维导电网络的柔性透明电极及电容传感器

为了开发具有优良性能的智能伪装隐身器件,使用预模板法制备了柔性透明电极.以叶脉纤维为预模板,在其表面沉积金属碳化物/氮化物（MXene）,从而开发了具有透明有序导电网络结构的透明电极.叶脉表面的羟基基团与导电材料的表面活性基团的相互作用极大地提高了导电材料与基底的表面结合力.此柔性透明电极在透光率为80.6%时,方阻为11.4Ω/sq,有效地避免了光电特性之间的“权衡”效应,且在1000次弯曲循环下电阻几乎保持不变,具备良好的耐久性和稳定性.将此透明电极成功制备透明电容式传感器,其灵敏度可达0.09 kPa^-1,且在1000次循环之后相对电容基本保持不变,具有出色的传感性能和耐久性,可以在人难以察觉的状态下监测人体运动信号.此柔性透明电极和透明电容传感器在可穿戴伪装电子领域具有巨大潜力.     

导电水凝胶的制备

作为一种新型的功能材料,导电水凝胶已经引起广泛的关注。本文根据目前的研究现状,将导电水凝胶大致分为聚电解质导电水凝胶,酸掺杂导电水凝胶,无机物添加导电水凝胶以及导电高分子基导电水凝胶等几大类,并综述了它们的制备方法。另外,由于大分子体系的导电高分子和水凝胶都有着独特和重要的性能,这使得它们具有广阔的应用价值。所以,本文在综述导电水凝胶制备进展的同时着重综述了导电高分子基导电水凝胶的制备进展。     

基于3D导电材料的柔性应力/应变传感器

柔性应力/应变传感器作为智能可穿戴设备的重要组成部分,在人体运动检测、健康监测、机器人和电子皮肤等方面得到了广泛应用.其中,3D导电材料(如气凝胶、海绵和泡沫等)不仅拥有3D互连微结构,还具有优异的可压缩性和导电性,在一定程度上解决了传感器同时拥有高灵敏度和宽检测限的难题.本文根据制备3D导电材料的原材料将其划分为生物...     

聚乙烯醇/聚吡咯复合导电水凝胶应变传感器的制备及性能

以聚乙烯醇(PVA)为原料, 植酸(PA)和氨基-聚倍半硅氧烷(NH₂-POSS, NP)为交联剂, 通过冻融循环法制得PVA/PA/NP复合水凝胶, 再以其为模板, 通过吡咯的原位聚合制得PVA/PA/NP-PPy复合导电水凝胶, 克服了聚吡咯材料易脆、 疏水的特性, 进一步改善了水凝胶的导电性和灵敏性. 循环拉伸实验结果表明该水凝胶具有良好的自回复能力, 电导率高达7.53 S/m, 从I-V曲线可知其作为柔性可穿戴应变传感器的最高检测电流可达 9.029 mA, 灵敏度因子可达6.796, I-T曲线表明该传感器可以准确地通过电流信号变化来监测人体的各种微小运动.     

软硬段交联共聚物基离子导电弹性体

通过一步点击聚合反应制备了软硬段交联共聚物基锂盐离子导电弹性体，其可作为柔性应变传感器用于监测手指弯曲和摩尔斯电码传输信息.硬段组分采用液晶基元，使膜在拉伸过程中分子趋于有序排列，增强弹性体的力学性能.软段组分采用聚乙二醇二甲基丙烯酸酯低聚物(M_n=750 g/mol)，不仅能增加离子导电弹性体的断裂伸长率和透明度，而且所含的醚氧链段能解离锂盐和传输锂离子，提高离子导电弹性体的导电率.通过优化组分间的比例能得到高应变灵敏度和循环稳定的离子导电弹性体.     

Design Strategies of Conductive Hydrogel for Biomedical Applications

Conductive hydrogel, with electroconductive properties and high water content in a three-dimensional structure is prepared by incorporating conductive polymers, conductive nanoparticles, or other conductive elements, into hydrogel systems through various strategies. Conductive hydrogel has recently attracted extensive attention in the biomedical field. Using different conductivity strategies, conductive hydrogel can have adjustable physical and biochemical properties that suit different biomedical needs. The conductive hydrogel can serve as a scaffold with high swelling and stimulus responsiveness to support cell growth in vitro and to facilitate wound healing, drug delivery and tissue regeneration in vivo. Conductive hydrogel can also be used to detect biomolecules in the form of biosensors. In this review, we summarize the current design strategies of conductive hydrogel developed for applications in the biomedical field as well as the perspective approach for integration with biofabrication technologies.     

Thin and high conductive multi-walled carbon nanotubes/polydimethylsiloxane composite film prepared via solvent method as strain sensors

Flexible strain sensors based on conductive fillers and flexible polymers possessed significant advantages in human motion detection. Preparing a strain sensing layer with high electrical conductivity and excellent mechanical property under high content of conductive filler contributed to the stability of flexible strain sensors. In this study, MWCNTs/PDMS composite film was prepared by the organic solvent method. The microstructure, electrical conductivity, mechanical property, and piezoresistive characteristics of the composite film at different MWCNTs contents were characterized and discussed. When the mass fraction of MWCNTs in the composite film was 5%, the composite film exhibited a high electrical conductivity of 9.56 S/m while maintaining ideal mechanical properties, and the film thickness was just about 180 μm. The relationship between electrical signals and film strain was performed. The piezoresistive characteristic results demonstrated that the prepared composite film could be used as flexible strain sensor for human motion detection. The prepared thin MWCNTs/PDMS composite film in this paper illustrated high conductive and desired flexibility, and was an alternative material for human motion detection.     

Thermally exfoliated graphene oxide reinforced stress responsive conductive nanocomposite hydrogel

Lightweight and flexible biosensors that can sustain mechanical deformation and can be adhered to human skin is an interesting field of study. In the current article, a systematic study on development of thermally exfoliated graphene oxide (TEGO)–reinforced poly(vinyl alcohol) (PVA)–based conductive hydrogel nanocomposites has been reported. The free‐standing hydrogels were synthesized using controlled and repetitive freeze‐thaw cycles. The samples were then studied for their mechanical as well as electrical properties. The hydrogels were characterized for their microstructural, chemical, and rheological properties to understand the observed macroscopic properties. Additionally, a study on the behavior of hydrogels immersed in phosphate‐buffered saline (PBS) was carried out to investigate their hydrolytic stability within simulated biological environment. Overall, the nanocomposite hydrogels demonstrated excellent static and dynamic mechanical performance, stability in PBS, considerable electrical conductivity, and significant electrical response to applied external stress, establishing their potential for use as flexible biosensors.     

MXene-composited highly stretchable,sensitive and durable hydrogel for flexible strain sensors

The flourishing development in flexible electronics has provoked intensive research in flexible strain sensors to realize accurate perception acquisition under different external stimuli.However,building hydrogel-based strain sensors with high stretchability and sensitivity remains a great challenge.Herein,MXene nanosheets were composited into polyacrylamide-sodium alginate matrix to construct mechanical robust and sensitive double networked hydrogel strain sensor.The hydrophilic MXene nanosheets formed strong interactions with the polymer matrix and endowed the hydrogel with excellent tensile properties(3150%),compliant mechanical strength(2.03 kPa~(-1) in Young's Module) and long-lasting stability and fatigue resistance(1000 dynamic cycles under 1,600% strain).Due to the highly oriented MXene-based three dimensional conductive networks,the hydrogel sensor achieved extremely high tensile sensitivity(18.15 in gauge factor) and compression sensitivity(0.38 kPa~(-1) below 3 kPa).MXene hydrogel-based strain sensors also displayed negligible hysteresis in electromechanical performance,typical frequent-independent feature and rapid response time to external stimuli.Moreover,the sensor exhibited accurate response to different scales of human movements,providing potential application in speech recognition,expression recognition and handwriting verification.     

Interpenetrating Network Hydrogels based on Nanostructured Conductive Polymers for Flexible Supercapacitor

Flexible conductive polymer hydrogels are unique material that synergize the features of conductive polymers and hydrogels. They are excellent candidates for the flexible supercapacitor electrodes. In this paper, flexible conductive polymer hydrogels were prepared with poly(vinyl alcohol) as soft skeleton through cyclic freezing-thawing method. Firstly, phytic acid-doped polyaniline with crosslinked network was prepared using phytic acid as the dopant and crosslinking agents. Hydrogels with interpenetrating binary network nanostructure were then formed by freezing-thawing method. The interpenetrating binary network structure endowed the hydrogel reliable mechanical properties with decent flexibility and compressive strength of 3.64 MPa. More importantly, this unique structure enable them to maintain highly specific capacitance (314 F/g at the current density of 0.5 A/g).     

Natural polymers-enhanced double-network hydrogel as wearable flexible sensor with high mechanical strength and strain sensitivity

Conductive hydrogels have shown great prospects as wearable flexible sensors. Nevertheless, it is still a challenge to construct hydrogel-based sensor with great mechanical strength and high strain sensitivity. Herein, an ion-conducting hydrogel was fabricated by introducing gelatin-dialdehyde β-cyclodextrin (Gel-DACD) into polyvinyl alcohol-borax (PVA-borax) hydrogel network. Natural Gel-DACD network acted as mechanical deformation force through non-covalent cross-linking to endow the polyvinyl alcohol-borax/gelatin-dialdehyde β-cyclodextrin hydrogel (PGBCDH) with excellent mechanical stress (1.35 MPa), stretchability (400%), toughness (1.84 MJ/m³) and great fatigue resistance (200% strain for 100 cycles). Surprisingly, PGBCDH displayed good conductivity of 0.31 S/m after adding DACD to hydrogel network. As sensor, it showed rapid response (168 ms), high strain sensitivity (gage factor (GF) = 8.57 in the strain range of 200%-250%) and reliable sensing stability (100% strain for 200 cycles). Importantly, PGBCDH-based sensor can accurately monitor complex body movements (knee, elbow, wrist and finger joints) and large-scale subtle movements (speech, swallow, breath and facial expressions). Thus, PGBCDH shows great potential for human monitoring with high precision.     

Flexible,stretchable and conductive PVA/PEDOT:PSS composite hydrogels prepared by SIPN strategy

Stretchable conductive hydrogels have received significant attention due to their possibility of being utilized in wearable electronics and healthcare devices. In this work, a semi-interpenetrating polymer network (SIPN) strategy was employed to fabricate a set of flexible, stretchable and conductive composite hydrogels composed of polyvinyl alcohol (PVA) in the presence of glutaraldehyde as the crosslinker, HCl as the catalyst and poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) as the conductive medium. The results from FTIR, Raman, SEM and TGA indicate that a chemical crosslinking network and interactions of PVA and PEDOT:PSS exist in the SIPN hydrogels. The swelling ratio of hydrogels decreased with increasing content of PEDOT:PSS. Due to the chemical crosslinking network and interactions of PVA and PEDOT:PSS, PVA networks semi-interpenetrated with PEDOT:PSS exhibited excellent tensile and compression properties. The tensile strength and elongation at breakage of the composite hydrogels with 0.14 wt% PEDOT:PSS were 70 KPa and 239%, respectively. The compression stress of the composite hydrogels with 0.14 wt% PEDOT:PSS at a strain of 50% was about 216 KPa. The electrical conductivity of the hydrogels increased with increasing PEDOT:PSS content. The flexible, stretchable and conductive properties endow the composite hydrogel sensor with a superior gauge factor of up to 4.4 (strain: 100%). Coupling the strain sensing capability to the flexibility, good mechanical properties and high electrical conductivity, we consider that the designed PVA/PEDOT:PSS composite hydrogels have promising applications in wearable devices, such as flexible electronic skin and sensitive strain sensors.     

复合材料柔软性对倒金字塔微结构阵列传感器性能的影响

采用模压成型方法制备了2种柔软性不同的热塑性聚氨酯/短切碳纤维/碳纳米管(TPU/SCF-CNT)复合材料复制物, 其表面上具有倒金字塔微结构阵列, 内部有SCF与CNT共同构成的导电通路. 将复合材料复制物和相应的复合材料平整片封装成柔性传感器. 结果表明, 压力作用下传感器内复制物和平整片之间的接触电阻因倒金字塔底棱的形变而显著降低. 对使用柔软性较高的复合材料封装的传感器, 虽然其相对迟滞稍大, 但压力作用下倒金字塔底棱形变量较大, 且复制物和平整片内导电通路增加量较大, 因此其在0~2.5 kPa的线性区内具有较高的灵敏度(0.32 kPa^?1). 制备的2种传感器均具有快速响应特性, 且能在500 s(约1580次)的循环压缩/释放测试(峰值压力约3 kPa)中保持较稳定的电阻响应. 研究表明, 利用模压成型的表面倒金字塔结构复合材料复制物封装成的柔性压力传感器具有良好的传感性能.