Research progress on moisturizing and anti-freezing conductive hydrogels in flexible electronics
-
摘要: 近年来，柔性电子材料得到了快速的发展，其中导电水凝胶由于其突出的导电性、柔韧性、亲肤性等已被广泛的应用于该领域。然而，类似于传统的水凝胶，大多数导电水凝胶在极端环境下仍面临应用受限的瓶颈问题。因此，许多学者对水凝胶的保湿/抗冻行为进行了研究，并设计制备了一系列保湿抗冻导电水凝胶。本文对近年来保湿抗冻导电水凝胶的制备策略进行了总结及归类，详细阐述其提升水凝胶温度适应性的潜在机制；重点对耐候型水凝胶在柔性电子领域的应用进行了综述，包括运动感知、健康监测、智能识别与人机交互等；并且对保湿抗冻导电水凝胶面临的机遇和挑战进行了探讨和展望，旨在为新型保湿抗冻导电水凝胶的构筑提供新的思路，可望开发出综合性能优异的导电水凝胶，进一步推动其在柔性电子领域中的实际应用。Abstract: Conductive hydrogel is one novel flexible material with outstanding conductivity, flexibility and skin-friendliness, which has made great progress in flexible electronics recently. However, similar to traditional hydrogels, the applications of conductive hydrogels in extreme environments still face limitations. To extend the operational temperature range of hydrogels, some researchers have paid attention to the dehydration/freezing behavior of hydrogels, resulting in the successful design and fabrication of a series of hydrogels with moisturizing and anti-freezing properties. In this review, the strategies for improving the temperature tolerance of hydrogels are summarized, and the potential mechanisms of moisturizing and anti-freezing hydrogels are described in detail. Furthermore, the applications of environmentally stable hydrogels in the field of flexible electronics are discussed, including motion perception, health monitoring, intelligent recognition and human-computer interaction. Additionally, the opportunities and challenges faced by the moisturizing and anti-freezing hydrogels are deliberated, with the objective of stimulating innovative approaches towards weather-resistant hydrogel development. By advancing the development of modern hydrogels with excellent comprehensive performance, the aim is to facilitate their broader practical application in extreme environments.
-
Key words:
- Conductive hydrogel /
- extreme environment /
- moisturizing /
- anti-freezing /
- flexible sensor
-
图 1 保湿抗冻水凝胶的设计策略及其应用
Figure 1. Design strategy and application of moisturizing and anti-freezing hydrogels.
图 6 (a) 基于SPGL水凝胶的应变传感器示意图和通过电路板实时监测人类颈椎运动[38]；(b) PCOBE-TENG的“三明治”结构示意图及其在单电极模式下的工作机制[48]
Figure 6. (a) Schematic diagram of the SPGL hydrogel-based strain sensor and real-time monitoring of human head bowing movement through the circuit board[38]. (b) The schematic diagram of the “sandwich” structure of PCOBE-TENG and its working mechanism in single-electrode mode[48].
图 9 (a) PBAPE电子皮肤智能手套手语与多种手势相结合的照片[54]；(b) 二维多功能人机界面进行检测及其应用[55]
Figure 9. (a) Photos of sign languages combined with multiple gestures and the signal curves corresponding to the five fingers collected by PBAPE e-skin smart glove[54]. (b) Detection using a two-dimensional multifunctional human–machine interface (2D-MHMI) and its application[55].
图 10 (a) SPOH光纤在激光传输中的应用[19]；(b) PVA/LNP水凝胶在100元人民币表面紫外线敏感荧光区的透明度和紫外线屏蔽能力[58]；(c) 有机水凝胶实现重复的信息记录和擦除[59]。
Figure 10. (a) Application of SPOH fibers in laser transmission[19]. (b) UV-shielding capabilities of PVA/LNP hydrogels on the UV-sensitive fluorescent area of the 100-yuan CNY surface[58]. (c) Photographs showing the organohydrogel can achieve repeated information recording and erasing[59].
表 1 各种水凝胶的保湿抗冻性能比较
Table 1. Comprehensive performance comparison of various moisturizing and antifreezing hydrogels
Conductive hydrogel Agent Moisturizing ability Anti-freezing ability References (PAAm)-F127DA Glycerol 60% (60℃, 34Days) −40℃ [20] CDPAP 1,3-propanediol ~80% (25℃, 20Days) −60℃ [40] PAA-CS-G/Gly Glycerol 80% (37℃, 15Days) −45℃ [41] PAM/carrageenan LiBr 87% (25℃, 4Days) −78.5℃ [42] P(AM-co-AA) LiCl 83.8% (50℃, 10 h) −20℃ [25] P(AA-co-DMAPS)/Al3+ Ionic liquid 97.2%(20℃, 60Days) −80℃ [33] P@P composite ionogel Ionic liquid 120℃ −58℃ [34] HPE-LiCl Ethylene glycol/LiCl 87% (25℃, 30Days)
79% (80℃, 100 h)−40℃ [38] PGN Glycerol/CaCl2 90% (28℃, 12Days) −20℃ [43] PHA/Agar/EG Ethylene glycol/NaCl 89% (25℃, 12Days) −40℃ [44] P(PEG-co-AA)/PANI Glycerol/PEG ~90% (20℃, 7Days)
~85% (40℃, 7Days)
~80% (80℃, 7Days)−28℃ [45] P(SBMA-co-AA) LiCl/zwitterionic polymer 100% (25℃, 7Days) −80°C [46] Notes: PAAm (PAM)-Polyacrylamide; F127DA-Pluronic F127Diacrylate; PAA-Poly(acrylic acid); CS-Chitosan; Gly-Glycerol; DMAPS-[2-(methacryloyloxy)ethyl] dimethyl-(3 sulfopropyl)ammonium hydroxide; PHA-poly(N-hydroxymethyl acrylamide); PEG-poly (ethylene glycol) methacrylate; PANI-Polyaniline; SBMA-Sulfobetaine methacrylate. 
下载: 导出CSV
-
[1] LI H, LV T, SUN H, et al. Ultrastretchable and superior healable supercapacitors based on a double cross-linked hydrogel electrolyte[J]. Nature Communications, 2019, 10(1): 536. doi: 10.1038/s41467-019-08320-z [2] PANJA S, DIETRICH B, ADAMS D J. Controlling syneresis of hydrogels using organic salts[J]. Angewandte Chemie International Edition, 2022, 61(4): e202115021. doi: 10.1002/anie.202115021 [3] XU J, JING R, REN X, et al. Fish-inspired anti-icing hydrogel sensors with low-temperature adhesion and toughness[J]. Journal of Materials Chemistry A, 2020, 8(18): 9373-9381. doi: 10.1039/D0TA02370A [4] 崔聪聪, 李汉红, 毛林韩, 等. 聚天冬氨酸/聚(丙烯酰胺-丙烯酸)/Fe3+离子水凝胶应变传感器的制备及在人体运动监测中的应用[J]. 高分子材料科学与工程, 2023, 39(3): 127-133.CUI Congcong, LI Hanhong, MAO Hanlin, et al. Preparation of polyaspartic acid/poly(acrylamide -acrylic acid)/Fe3+ ionic hydrogel strain sensor and its application in human motion monitoring[J]. Polymer Materials Science & Engineering, 2023, 39(3): 127-133 (in Chinese). [5] HU Y, ZHUO H, ZHANG Y, et al. Graphene oxide encapsulating liquid metal to toughen hydrogel[J]. Advanced Functional Materials, 2021: 2106761. [6] ZHANG M, YU R, TAO X, et al. Mechanically robust and highly conductive ionogels for soft ionotronics[J]. Advanced Functional Materials, 2022, 33(10): 2208083. [7] FAN X, KE T, GU H. Multifunctional, ultra-tough organohydrogel e-skin reinforced by hierarchical goatskin fibers skeleton for energy harvesting and self-powered monitoring[J]. Advanced Functional Materials, 2023, 33(42): 2304015. doi: 10.1002/adfm.202304015 [8] 杨羽歆, 周祥富, 郑丹丹, 等. 原位法制备聚乙二醇/聚(丙烯酰胺-co-丙烯酸)荧光水凝胶[J]. 高分子材料科学与工程, 2022, 38(6): 153-160.YANG Yuxin, ZHOU Xiangfu, ZHENG Dandan, et al. , In-situ preparation of polyethylene glycol/poly (acrylamide-co-acrylic acid) fluorescent hydrogel[J]. Polymer Materials Science & Engineering, 2022, 38(6): 153-160 (in Chinese). [9] ZHOU L, DAI C, FAN L, et al. Injectable self-healing natural biopolymer-based hydrogel adhesive with thermoresponsive reversible adhesion for minimally invasive surgery[J]. Advanced Functional Materials, 2021, 31(14): 2007457. doi: 10.1002/adfm.202007457 [10] 高建朋, 明李, 唐佩福. 刺激响应型水凝胶在骨修复中的应用综述[J]. 解放军医学院学报, 2021, 42(8): 873-877. doi: 10.3969/j.issn.2095-5227.2021.08.016GAO Jianpeng, MING Li, TANG Peifu. Research advances in application of stimuli-responsive hydrogels in bone repairation[J]. Academic Journal of Chinese PLA Medical School, 2021, 42(8): 873-877 (in Chinese). doi: 10.3969/j.issn.2095-5227.2021.08.016 [11] 谢竺航, 李金宝, 修慧娟, 等. OS-PVA/P(DMC-AM)双网络水凝胶的制备及其吸附性能研究[J]. 中国造纸, 2021, 40(10): 37-43.XIE Zhuhang, LI Jinbao, XIU Huijuan, et al. Preparation and adsorption properties of OS-PVA/ P(DMC-AM) double network hydrogel[J]. China Pulp & Paper, 2021, 40(10): 37-43 (in Chinese). [12] KANG M, ODERINDE O, HAN X, et al. Development of oxidized hydroxyethyl cellulose-based hydrogel enabling unique mechanical, transparent and photochromic properties for contact lenses[J]. International Journal of Biological Macromolecules, 2021, 183: 1162-1173. doi: 10.1016/j.ijbiomac.2021.05.029 [13] XU S, ZHOU Z, LIU Z, et al. Concurrent stiffening and softening in hydrogels under dehydration[J]. Science Advances, 2023, 9: 3240. doi: 10.1126/sciadv.ade3240 [14] RONG Q, LEI W, CHEN L, et al. Anti-freezing, conductive self-healing organohydrogels with stable strain-sensitivity at subzero temperatures[J]. Angewandte Chemie International Edition, 2017, 56(45): 14159-14163. doi: 10.1002/anie.201708614 [15] ZHOU X, ZHAO F, GUO Y, et al. Architecting highly hydratable polymer networks to tune the water state for solar water purification[J]. Science Advances, 2019, 5: 5484. doi: 10.1126/sciadv.aaw5484 [16] XU C, YANG K, ZHU G, et al. Anti-freezing multifunctional conductive hydrogels: From structure design to flexible electronic devices[J]. Materials Chemistry Frontiers, 2024, 8(2): 381-403. doi: 10.1039/D3QM00902E [17] JIAN Y, WANG S, ZHANG J, et al. Biomimetic anti-freezing polymeric hydrogels: Keeping soft-wet materials active in cold environments[J]. Materials Horizons, 2021, 8(2): 351-369. doi: 10.1039/D0MH01029D [18] XIE Y, GAO S, JIAN J J, et al. Skin-mimicking strategy to fabricate strong and highly conductive anti-freezing cellulose-based hydrogels as strain sensors[J]. International Journal of Biological Macromolecules, 2023, 227: 462-471. doi: 10.1016/j.ijbiomac.2022.12.079 [19] ZHU L, XU J, SONG J, et al. Transparent, stretchable and anti-freezing hybrid double-network organohydrogels[J]. Science China Materials, 2022, 65(8): 2207-2216. doi: 10.1007/s40843-021-1961-1 [20] SUN Y, LU S, DU Y, et al. Long-lasting moisture and anti-freezing tough organohydrogels based on multi-functional nano-micelles for flexible dual-response sensors[J]. Journal of Applied Polymer Science, 2022, 139(38): 52916. doi: 10.1002/app.52916 [21] WU M, CHEN B, FAN X, et al. Liquid-metals-induced formation of MXene/ polyacrylamide composite organohydrogels for wearable flexible electronics[J]. Nano Research, 2023, 17: 1913-1922. [22] Li M, Chen D, Sun X, et al. An environmentally tolerant, highly stable, cellulose nanofiber-reinforced, conductive hydrogel multifunctional sensor[J]. Carbohydrate Polymers, 2022, 284: 119199. doi: 10.1016/j.carbpol.2022.119199 [23] 王海朋, 蔡文生, 邵学广. 抗冻剂抗冻机制的近红外光谱与分子模拟研究[J]. 化学学报, 2023, 81(9): 1167. doi: 10.6023/A23040185WANG Haipeng, CAI Wensheng, SHAO Xueguang. Antifreeze mechanism of antifreeze agents by near infrared spectroscopy and molecular simulations[J]. Acta Chimica Sinica, 2023, 81(9): 1167 (in Chinese). doi: 10.6023/A23040185 [24] WANG C, LIU Y, QU X, et al. Ultra-stretchable and fast self-healing ionic hydrogel in cryogenic environments for artificial nerve fiber[J]. Advanced Materials, 2022, 34(16): 2105416. doi: 10.1002/adma.202105416 [25] CAI H, ZHANG D, ZHANG H, et al. Trehalose-enhanced ionic conductive hydrogels with extreme stretchability, self-adhesive and anti-freezing abilities for both flexible strain sensor and all-solid-state supercapacitor[J]. Chemical Engineering Journal, 2023, 472: 144849. doi: 10.1016/j.cej.2023.144849 [26] SONG Y, NIU L, MA P, et al. Rapid preparation of antifreezing conductive hydrogels for flexible strain sensors and supercapacitors[J]. ACS Applied Materials & Interfaces, 2023, 15(7): 10006-10017. [27] FENG E, ZHANG M, LI X, et al. Mechanically toughed and self-adhesive organohydrogel with anti-freezing and non-drying properties for human motion monitoring and information transmission[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2024, 682: 132992. doi: 10.1016/j.colsurfa.2023.132992 [28] ZHANG X, LIANG S, LI F, et al. Flexible strain-sensitive sensors assembled from mussel-inspired hydrogel with tunable mechanical properties and wide temperature tolerance in multiple application scenarios[J]. ACS Applied Materials & Interfaces, 2023, 15(43): 50400-50412. [29] CHEN D, ZHAO X, WEI X, et al. Ultrastretchable, tough, antifreezing, and conductive cellulose hydrogel for wearable strain sensor[J]. ACS Applied Materials & Interfaces, 2020, 12(47): 53247-53256. [30] FAN X, LIU S, JIA Z, et al. Ionogels: Recent advances in design, material properties and emerging biomedical applications[J]. Chemical Society Reviews, 2023, 52(7): 2497-2527. doi: 10.1039/D2CS00652A [31] LIU J, ZHANG X, CUI Y, et al. Ionic liquid/water binary solvent anti-freezing hydrogel for strain and temperature sensors[J]. ACS Applied Materials & Interfaces, 2024, 16(4): 5208-5216. [32] ZHOU Y, FEI X, TIAN J, et al. A ionic liquid enhanced conductive hydrogel for strain sensing applications[J]. Journal of Colloid and Interface Science, 2022, 606: 192-203. doi: 10.1016/j.jcis.2021.07.158 [33] ZHANG X, CUI C, CHEN S, et al. Adhesive ionohydrogels based on ionic liquid/water binary solvents with freezing tolerance for flexible ionotronic devices[J]. Chemistry of Materials, 2022, 34(3): 1065-1077. doi: 10.1021/acs.chemmater.1c03386 [34] YANG J, CHANG L, MA C, et al. Highly electrically conductive flexible ionogels by drop-casting ionic liquid/PEDOT: PSS composite liquids onto hydrogel networks[J]. Macromolecular Rapid Communications, 2022, 43(1): e2100557. doi: 10.1002/marc.202100557 [35] WANG Y, YAO A, DOU B, et al. Self-healing, environmentally stable and adhesive hydrogel sensor with conductive cellulose nanocrystals for motion monitoring and character recognition[J]. Carbohydrate Polymers, 2024, 332: 121932. doi: 10.1016/j.carbpol.2024.121932 [36] WANG Q, LIANG X, SHEN L, et al. Double cross-linked hydrogel dressings based on triblock copolymers bearing antifreezing, antidrying, and inherent antibacterial properties[J]. Biomacromolecules, 2024, 25(1): 388-399. doi: 10.1021/acs.biomac.3c01040 [37] PENG H, HAO L, ZHANG X, et al. Zwitterion-incorporated antifreeze hydrogel with highly stretchable, transparent, and self-adhesive properties for flexible strain sensors[J]. ACS Applied Polymer Materials, 2024, 6(3): 1911-1921. doi: 10.1021/acsapm.3c02749 [38] WANG Y, LIU H, YU J, et al. Ionic conductive cellulose-based hydrogels with superior long-lasting moisture and antifreezing features for flexible strain sensor applications[J]. Biomacromolecules, 2024, 25(2): 838-852. doi: 10.1021/acs.biomac.3c01011 [39] LIU R, LIU Y, FU S, et al. Humidity adaptive antifreeze hydrogel sensor for intelligent control and human-computer interaction[J]. Small, 2024: 2308092. [40] LING Q, FAN X, LING M, et al. Collagen-based organohydrogel strain sensor with self-healing and adhesive properties for detecting human motion[J]. ACS Applied Materials & Interfaces, 2023, 15(9): 12350-12362. [41] ZHANG Y, LI Q, CHEN J, et al. Rapid gelation of dual physical network hydrogel with ultra-stretchable, antifreezing, moisturing for stable and sensitive response[J]. Journal of Applied Polymer Science, 2023, 140(10): 53566. doi: 10.1002/app.53566 [42] WU Z, SHI W, DING H, et al. Ultrastable, stretchable, highly conductive and transparent hydrogels enabled by salt-percolation for high-performance temperature and strain sensing[J]. Journal of Materials Chemistry C, 2021, 9(39): 13668-13679. doi: 10.1039/D1TC02506F [43] LI Y, Hu C, LAN J, et al. Hydrogel-based temperature sensor with water retention, frost resistance and remoldability[J]. Polymer, 2020, 186: 122027. doi: 10.1016/j.polymer.2019.122027 [44] YANG J, KANG Q, ZHANG B, et al. Strong, tough, anti-freezing, non-drying and sensitive ionic sensor based on fully physical cross-linked double network hydrogel[J]. Materials Science & Engineering C, 2021, 130: 112452. [45] YU X, ZHANG H, WANG Y, et al. Highly stretchable, ultra-soft, and fast self-healable conductive hydrogels based on polyaniline nanoparticles for sensitive flexible sensors[J]. Advanced Functional Materials, 2022, 32(33): 2204366. doi: 10.1002/adfm.202204366 [46] SUI X, GUO H, CAI C, et al. Ionic conductive hydrogels with long-lasting antifreezing, water retention and self-regeneration abilities[J]. Chemical Engineering Journal, 2021, 419: 129478. doi: 10.1016/j.cej.2021.129478 [47] TAO X, ZHU K, CHEN H, et al. Recyclable, anti-freezing and anti-drying silk fibroin-based hydrogels for ultrasensitive strain sensors and all-hydrogel-state super-capacitors[J]. Materials Today Chemistry, 2023, 32: 101624. doi: 10.1016/j.mtchem.2023.101624 [48] SONG B, FAN X, SHEN J, et al. Ultra-stable and self-healing coordinated collagen-based multifunctional double-network organohydrogel E-skin for multimodal sensing monitoring of strain-resistance, bioelectrode, and self-powered triboelectric nanogenerator[J]. Chemical Engineering Journal, 2023, 474: 145780. doi: 10.1016/j.cej.2023.145780 [49] SHI Y, GUAN Y, LIU M, et al. Tough, antifreezing, and piezoelectric organohydrogel as a flexible wearable sensor for human-machine interaction[J]. ACS Nano, 2024, 18(4): 3720-3732. doi: 10.1021/acsnano.3c11578 [50] LI J, GE S, NIU Y, et al. Intrinsically adhesive, conductive organohydrogel with high stretchable, moisture retention, anti-freezing and healable properties for monitoring of human motions and electrocardiogram[J]. Sensors and Actuators: B. Chemical, 2023, 377: 133098. doi: 10.1016/j.snb.2022.133098 [51] LU Y, YUE Y, DING Q, et al. Environment-tolerant ionic hydrogel-elastomer hybrids with robust interfaces, high transparence, and biocompatibility for a mechanical-thermal multimode sensor[J]. InfoMat, 2023, 5(4): 12409. doi: 10.1002/inf2.12409 [52] PANG J, WANG L, XU Y, et al. Skin-inspired cellulose conductive hydrogels with integrated self-healing, strain, and thermal sensitive performance[J]. Carbohydrate Polymers, 2020, 240: 116360. doi: 10.1016/j.carbpol.2020.116360 [53] MIAO Z, SONG Y, DONG Y, et al. Intrinsic conductive cellulose nanofiber induce room-temperature reversible and robust polyvinyl alcohol hydrogel for multifunctional self-healable biosensors[J]. Nano Research, 2022, 16(2): 3156-3167. [54] SONG B, DAI X, FAN X, et al. Wearable multifunctional organohydrogel-based electronic skin for sign language recognition under complex environments[J]. Journal of Materials Science & Technology, 2024, 181: 91-103. [55] WU W, REN Y, JIANG T, et al. Anti-drying, transparent, ion-conducting, and tough organohydrogels for wearable multifunctional human-machine interfaces[J]. Chemical Engineering Journal, 2022, 430: 132635. doi: 10.1016/j.cej.2021.132635 [56] 范克凡, 李鲲, 杨志坚, 等. 双网络MXene水凝胶的制备及其电磁和紫外屏蔽性能[J]. 复合材料学报, 2023, 40(7): 3939.FAN Kefan, LI Kun, YAN Zhijian, et al. Preparation of dual-network MXene hydrogels and their electromagnetic and UV shielding properties[J]. Acta Materiae Compositae Sinica, 2023, 40(7): 3939 (in Chinese). [57] 王钦雯, 王雯君, 陈玟锦, 等. 纳米银/纳米纤维素复合抗菌应变响应性水凝胶[J]. 复合材料学报, 2023, 42: 1.WANG Qinwen, WANG Wenjun, CHEN Wenjin, et al. Silver nanoparticle/nanocellulose composites antibacterial strain-responsive hydrogels[J]. Acta Materiae Compositae Sinica, 2023, 42: 1 (in Chinese). [58] WANG Y, LIU S, WANG Q, et al. Nanolignin filled conductive hydrogel with improved mechanical, anti-freezing, UV-shielding and transparent properties for strain sensing application[J]. International Journal of Biological Macromolecules, 2022, 205: 442-451. doi: 10.1016/j.ijbiomac.2022.02.088 [59] ZHENG G, GAO W, LI X, et al. A kappa-carrageenan-containing organohydrogel with adjustable transmittance for an antifreezing, nondrying, and solvent-resistant strain sensor[J]. Biomacromolecules, 2022, 23(11): 4872-4882. doi: 10.1021/acs.biomac.2c01044 -
下载:
点击查看大图
计量
- 文章访问数: 81
- HTML全文浏览量: 33
- 被引次数: 0
