高强度耐低温纳米纤维素/聚乙烯醇导电复合水凝胶制备及其在柔性传感中的应用

胡魁; 王映月; 王昊昱; 赵志鹏; 刘凯; 黄六莲; 陈礼辉

doi:10.13801/j.cnki.fhclxb.20220322.003

高强度耐低温纳米纤维素/聚乙烯醇导电复合水凝胶制备及其在柔性传感中的应用

doi: 10.13801/j.cnki.fhclxb.20220322.003

福建农林大学　材料工程学院，福州 350100

基金项目: 国家自然科学基金面上项目(32171733)；福建省自然科学基金项目(2021J01102)

详细信息

通讯作者:
刘凯，博士，副教授，硕士生导师，研究方向为生物质复合材料　E-mail: liuk1103@fafu.edu.cn

中图分类号: TB332；TQ427.7
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出版历程
- 收稿日期: 2022-01-21
- 修回日期: 2022-03-02
- 录用日期: 2022-03-09
- 网络出版日期: 2022-03-23
- 刊出日期: 2023-02-15

Preparation of high-strength and low-temperature-resistant nanocellulose/polyvinyl alcohol conductive composite hydrogel and its application in flexible sensing

College of Materials Engineering, Fujian Agriculture and Forestry University, Fuzhou 350100, China

Funds: National Natural Science Foundation of China (32171733); Natural Science Foundation of Fujian Province (2021J01102)

摘要

摘要: 纳米纤维素具有大长径比、较高的弹性模量与比表面积及丰富的表面官能团，是一种优良的纳米增强材料。首先以纳米纤维素(CNFs)为分散介质辅助分散MXene纳米片层，制备CNF-MXene纳米复合物，并通过FTIR与XPS分析CNFs与MXene的相互作用。以此复合物为增强填料，聚乙烯醇(PVA)为基底，制备CNF-MXene/PVA复合水凝胶，进一步通过KOH溶液处理，提高复合水凝胶的力学性能，并赋予复合水凝胶优异的离子导电性。该复合水凝胶表现出优异的力学性能，其拉伸强度与断裂伸长率分别达到255.9 kPa与1098.2%，还具有高电导率(2.38 S/m)、一定的抗冻性能与灵敏的应变/压力响应性。基于该复合水凝胶组装的应变/压力柔性传感器，由于具有极低的检测极限质量(100 mg)与极快的响应时间(225 ms)，可以监控脉搏跳动与喉咙发声微小震动引起的压力变化。因此，该复合水凝胶基柔性传感器非常有希望应用于未来新一代可穿戴电子、人机交互等领域。
- 聚乙烯醇 /
- 纳米纤维素 /
- 复合水凝胶 /
- 传感性能 /
- 柔性传感器
Abstract: Nanocellulose is an excellent nano-reinforcing material with large aspect ratio, high elastic modulus and specific surface area, and abundant surface functional groups. Nanocellulose (cellulose nanofibers, CNFs) was first used as the dispersion medium to disperse the MXene nanosheets for preparing the nanocellulose/MXene nanocomposites, and the interaction between nanocellulose and MXene was characterized and analyzed by FTIR and XPS. Then the CNF-MXene/PVA composite hydrogel was prepared by using the CNF-MXene nanocomposites as the reinforcing filler and polyvinyl alcohol (PVA) as the matrix, which was further treated with KOH solution to improve the mechanical properties of the composite hydrogel and endow the composite hydrogel with excellent ionic conductivity. The composite hydrogel exhibites excellent mechanical properties, the tensile strength and elongation at break were 22.5 kPa and 1098.2%, respectively. The hydrogel also possesses high conductivity (2.38 S/m), anti-freezing, and excellent strain/pressure responsive properties. Thanks to the extremely low detection limit (100 mg) and extremely fast response time (225 ms), the hydrogel-based strain/pressure sensor could monitor the pressure changes causes by pulse beating and small vibration of throat. Therefore, the composite hydrogel-based flexible sensor showes great promising applications in the next-generation wearable electronics and human-machine interaction.
- polyvinyl alcohol /
- nanocellulose /
- composite hydrogel /
- sensing property /
- flexible sensor

HTML全文

图 1 (a) 纳米纤维素(CNFs)-MXene/聚乙烯醇(PVA)-KOH复合水凝胶制备流程图；(b) CNF-MXene/PVA-KOH复合水凝胶内部结构示意图；PVA (c)和CNF-MXene/PVA-KOH水凝胶(d)的横截面SEM图像

Figure 1. (a) Preparation process of cellulose nanofibers (CNFs)-MXene/polyvinyl alcohol (PVA)-KOH composite hydrogels; (b) Schematic diagram of the internal structure of the CNF-MXene/PVA-KOH composite hydrogels; SEM images of the cross-section of PVA hydrogel (c) and CNF-MXene/PVA-KOH composite hydrogel (d)

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图 2 (a) MXene及CNF-MXene复合物在水中静置不同时间后的对比照片；(b) CNFs、MXene与CNF-MXene复合物的FTIR图谱；CNF-MXene复合物的Ti2p (c)与O1s (d) XPS图谱

Figure 2. (a) Photos of the MXene and CNF-MXene suspensions after standing in water for different times; (b) FTIR spectra of CNFs, MXene and CNF-MXene nanocomposites; XPS Ti2p (c) and O1s (d) spectra of CNF-MXene nanocomposites

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图 3 PVA、CNF-MXene/PVA、CNF-MXene/PVA-KOH水凝胶的拉伸应力-应变曲线(a)、杨氏模量和拉伸强度(b)、压缩应力-应变曲线(c)与韧性(d)

Figure 3. Tensile stress-strain curves (a), Young's modulus and tensile strength (b), compressive stress-strain curves (c) and toughness (d) of PVA, CNF-MXene/PVA and CNF-MXene/PVA-KOH hydrogels

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图 4 PVA、CNF-MXene/PVA 与CNF-MXene/PVA-KOH水凝胶的电导率

Figure 4. Conductivities of the PVA, CNF-MXene/PVA and CNF-MXene/PVA-KOH hydrogels

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图 5 PVA、CNF-MXene/PVA与CNF-MXene/PVA-KOH水凝胶的保水率

Figure 5. Water retention of the PVA, CNF-MXene/PVA and CNF-MXene/PVA-KOH hydrogels

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图 6 (a) CNF-MXene/PVA与CNF-MXene/PVA-KOH水凝胶在室温和冷冻后的对比；(b) PVA、CNF-MXene/PVA与CNF-MXene/PVA-KOH水凝胶的DSC图谱

Figure 6. (a) Comparison photos of the CNF-MXene/PVA and CNF-MXene/PVA-KOH hydrogels at room temperature and after freezing; (b) DSC spectra of the PVA, CNF-MXene/PVA and CNF-MXene/PVA-KOH hydrogels

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图 7 (a) CNF-MXene/PVA-KOH水凝胶基传感器对反复慢速与快速拉伸的响应性；(b)水凝胶传感器对反复20%与40%拉伸应变的响应性

ΔR/R₀—Relative resistance changes

Figure 7. (a) Response of the CNF-MXene/PVA-KOH hydrogel-based sensor to repeated slow and fast stretching; (b) Response of the hydrogel-based sensor to loading of 20% and 40% strain

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图 8 (a)CNF-MXene/PVA-KOH水凝胶基传感器对外界质量的响应时间与检测极限；(b)水凝胶传感器对不同质量压力的响应性；(c)水凝胶传感器对手腕脉搏跳动的响应性；(d)水凝胶传感器对说“FAFU”引起的喉咙震动的响应性

Figure 8. (a) Measurement results of the response time and detection limit of the CNF-MXene/PVA-KOH hydrogel-based sensor; (b) Response of the hydrogel-based sensor to different weights on its surface; (c) Response of the hydrogel-based sensor to the wrist pulse beating; (d) Response of the hydrogel-based sensor to the throat vibration induced by speaking “FAFU”

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