High toughness and self-healing conductive hydrogels of chitosan-poly acrylic acid-MXene and capability for strain sensors
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摘要: 壳聚糖基导电水凝胶在电子皮肤、健康监测和柔性穿戴电子等领域得到广泛关注。本文将MXene分散到丙烯酸-壳聚糖水溶液中，丙烯酸原位聚合成聚丙烯酸，制备了壳聚糖-聚丙烯酸-MXene导电水凝胶(CS-PAA-MXene)。CS-PAA-MXene具有优异的力学性能，其断裂应变为1450%，断裂应力为0.6 MPa，韧性达到2.6 MJ·m−3。CS-PAA-MXene能够粘附于多种物体表面，包括玻璃、塑料、橡胶、铜片和铝片等，其中对玻璃的最大剥离力可达到175 N·m−1；CS-PAA-MXene具有优异的自修复性能，切断的CS-PAA-MXene相互接触2.5 s后，其电阻恢复到切断前数值。CS-PAA-MXene应变传感器被成功用于检测人体各类活动，如手指、手肘和膝盖等关节弯曲活动。基于壳聚糖的阳离子电荷及其抗菌特性，CS-PAA-MXene将在自粘附和高延展的柔性传感器具有良好的应用前景。Abstract: Chitosan-based conductive hydrogels have attracted extensive attention in electronic skins, human health monitoring, and flexible wearable sensors. In this work, MXene was dispersed in acrylic acid-chitosan solution, and then the acrylic acid monomer was in situ polymerized to synthesis the chitosan-poly(acrylic acid)-MXene hydrogels (CS-PAA-MXene). CS-PAA-MXene shows excellent mechanical properties. The tensile strength of the CS-PAA-MXene is as high as 0.6 MPa, and its elongation at break and toughness reach 1450% and 2.6 MJ·m−3, respectively. CS-PAA-MXene can adhere to various surfaces, including glass, plastic, rubber, copper and aluminum, etc. The maximum peeling force on the glass can reach 175 N·m−1. After the cut CS-PAA-MXene contacts each other for 2.5 s, its resistance value returns to the pre-cut value, suggesting CS-PAA-MXene has excellent self-healing performance. CS-PAA-MXene strain sensors have been successfully used to detect a wide range of human movements, such as the joint flexions of finger, elbow and knee. Due to the cationic charge and antibacterial properties of chitosan, CS-PAA-MXene conductive hydrogels will have a good application prospect in self-adhesive and high-extensibility flexible sensors.
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Key words:
- chitosan /
- MXene /
- conductive hydrogels /
- mechanical properties /
- strain sensor
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图 1 (a) 壳聚糖-聚丙烯酸-MXene水凝胶(CS-PAA-MXene)的制备过程和网络结构示意图；(b) CS-PAA-MXene水凝胶的氢键相互作用示意图
Figure 1. (a) Schematic preparation process and network structure of chitosan-poly(acrylic acid)-MXene hydrogels (CS-PAA-MXene); (b) Schematic of hydrogen bond interaction of CS-PAA-MXene hydrogel
KPS—Potassium persulfate; AAc—Acrylic acid; Gly—Glycerol; MBA—N, N'-methylene diacrylamide
图 2 CS、CS-PAA、CS-PAA-MXene水凝胶的FTIR图谱(a)；CS-PAA-MXene水凝胶的C1s (b)和 Ti2p (c)的XPS图谱
Figure 2. FTIR spectra of CS, CS-PAA and CS-PAA-MXene hydrogel (a); High-resolution XPS spectra of C1s (b) and Ti2p (c) region of CS-PAA-MXene hydrogel
图 3 水凝胶的SEM图像：(a) CS-PAA表面；(b) CS-PAA截面；(c) CS-PAA-MXene表面；(d) CS-PAA-MXene截面
Figure 3. SEM images of hydrogels: (a) CS-PAA surface; (b) CS-PAA section; (c) CS-PAA-MXene surface; (d) CS-PAA-MXene section
图 4 (a) CS-PAA和CS-PAA-MXene水凝胶的应力-应变曲线；(b) CS-PAA和CS-PAA-MXene水凝胶的弹性模量与韧性；(c) CS-PAA-MXene水凝胶及其扭转和拉伸的照片；(d) 本工作与类似水凝胶材料的韧性和断裂应力对比图[33-37]
Figure 4. (a) Tensile stress-strain curves of the CS-PAA and CS-PAA-MXene hydrogels; (b) Elastic modulus and toughness of the CS-PAA and CS-PAA-MXene hydrogels; (c) Photos of CS-PAA-MXene hydrogel and its torsion and stretching; (d) Comparison diagram of toughness and fracture stress of this work and similar hydrogel materials[33-37]
PAN—Polyacrylonitrile; SA—Sodium alginate
图 5 (a) CS-PAA-MXene水凝胶粘附于玻璃、塑料、橡胶、铝片、铜片、木材的照片；(b) 粘附性能测试示意图；(c) CS-PAA-MXene水凝胶对不同物体的粘附性能
Figure 5. (a) Photos of CS-PAA-MXene hydrogel adhering to glass, plastic, rubber, aluminum sheet, copper sheet and wood; (b) Schematic diagram of adhesion performance test; (c) Adhesion performance of CS-PAA-MXene hydrogel in different substrates
图 6 (a) 实时测量CS-PAA-MXene水凝胶在切割愈合过程中的电阻恢复周期；(b) CS-PAA-MXene水凝胶切割后的自修复行为(LED在水凝胶切割-修复后亮度变化)
Figure 6. (a) Resistance recovery of the CS-PAA-MXene hydrogel during the cutting-healing cycle; (b) Self-healing behavior of the CS-PAA-MXene hydrogel after cutting (Brightness change of LED under the cutting healing process)
图 7 CS-PAA-MXene水凝胶对人体运动传感：(a) 灵敏度(GF)值；(b) 手指弯曲；(c) 手肘弯曲；(d) 膝盖弯曲
Figure 7. Human motion sensing of CS-PAA-MXene hydrogel: (a) Sensitivity (GF) value; (b) Finger bending; (c) Elbow bending; (d) Knee bending
ΔR/R0—Change ratio of resistance
表 1 不同MXene浓度的样品名称
Table 1. Sample names for different MXene concentrations
Sample Concentration of MXene in glycerol
aqueous solution/(mg·mL−1)CS-PAA 0 CS-PAA-MXene1 1 CS-PAA-MXene5 5 CS-PAA-MXene10 10 
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