多环境稳定抗溶胀凝胶的高通量制备及其在柔性传感器的应用

  水凝胶材料通常具有高水含量、柔软性和生物兼容性等独特性质，因此基于导电水凝胶的可穿戴生物电子柔性传感器备受关注。在电子设备应用场景多样化的需求刺激下，开发多环境（高湿度、高温等）稳定性的导电水凝胶成为研究趋势。然而，传统水凝胶传感器普遍存在一些问题，如难以实现在多种溶剂（极性、非极性溶剂）和极端温度下，仍长期保有稳定的力学、电学性能。此外，传统的水凝胶材料开发过程存在速度慢、研发周期长和成本高等问题。

  针对上述问题，本文结合材料高通量实验法，利用课题组自制的高通量化学反应装置，在二元溶剂（醇溶剂/水）中引入了盐酸多巴胺(DA)和硅酸锂镁盐纳米片(LAPONITE)分散液，并通过自由基聚合对甲基丙烯酸羟乙酯(HEMA)、丙烯酰胺(AAm)和N,N'-亚甲基双丙烯酰胺(BIS)进行共聚来制备具有多种键合效应的无机-有机复合网络凝胶。其中二元溶剂和HEMA有效地改善了凝胶的抗溶胀和耐干燥性，DA明显地增强凝胶的水下粘附性(水环境中长时间维持在40 kPa)，LAPONITE则显著提高了凝胶的模量(19.3 kPa)。

  本文为实现有机凝胶的传感器应用，通过引入羟基化的碳纳米管(CNT)增强了其导电性能。最终制备得到的有机凝胶显示出高导电性(1.0 mS/cm)和优异的灵敏度(GF=3.68)，在极宽的应变范围(0.5-600%)内仍能保持稳定的信号，因此能够精确地检测和响应微小的压力和形变。抗溶胀和抗冻特性使其在-20~50℃的温度范围内仍能进行精确的人体指关节弯曲检测，从而实现水下加密通信功能。它还可以作为电极来集成到可穿戴无线设备中，实现水下监测心率的功能。综上所述，本论文综合多种凝胶性能改善策略进行筛选实验后，制备得到的多环境稳定有机凝胶可实现多环境传感应用，同时也实现了高分子凝胶的批量制备，这为开发多环境适应性的软生物电子材料提供了一种简单而有效的策略。

[1] YUK H, LU B, ZHAO X. Hydrogel Bioelectronics [J]. Chemical Society Reviews, 2019, 48(6): 1642-1667.
[2] ZHU Y, ZHANG J, SONG J, et al. A Multifunctional Pro‐Healing Zwitterionic Hydrogel for Simultaneous Optical Monitoring of pH and Glucose in Diabetic Wound Treatment [J]. Advanced Functional Materials, 2020, 30(6): 1905493.
[3] YANG J C, MUN J, KWON S Y, et al. Electronic Skin: Recent Progress and Future Prospects for Skin-Attachable Devices for Health Monitoring, Robotics, and Prosthetics [J]. Advanced Materials, 2019, 31(48): 1904765.
[4] CHEN D, PEI Q. Electronic Muscles and Skins: A Review of Soft Sensors and Actuators [J]. Chemical Reviews, 2017, 117(17): 11239-11268.
[5] PEREZ A J, ZEADALLY S. Recent Advances in Wearable Sensing Technologies [J]. Sensors:Basel, 2021, 21(20): 6828.
[6] FU H, WANG B, LI J, et al. A Self-healing, Recyclable and Conductive Gelatin/nanofibrillated Cellulose/Fe3+ Hydrogel Based on Multi-dynamic Interactions for a Multifunctional Strain Sensor [J]. Materials Horizons, 2022, 9(5): 1412-1421.
[7] LIANG X, CHEN G, LIN S, et al. Bioinspired 2D Isotropically Fatigue-Resistant Hydrogels [J]. Advanced Materials, 2022, 34(8): e2107106.
[8] ZENG S, ZHANG J, ZU G, et al. Transparent, Flexible, and Multifunctional Starch-based Double-network Hydrogels as High-performance Wearable Electronics [J]. Carbohydrate Polymers, 2021, 267: 118198.
[9] YUK H, WU J, ZHAO X. Hydrogel Interfaces for Merging Humans and Machines [J]. Nature Reviews Materials, 2022, 7(12): 935-952.
[10] GAO W, OTA H, KIRIYA D, et al. Flexible Electronics toward Wearable Sensing [J]. Accounts of Chemical Research, 2019, 52(3): 523-533.
[11] FAN H, WANG J, TAO Z, et al. Adjacent Cationic-aromatic Sequences Yield Strong Electrostatic Adhesion of Hydrogels in Seawater [J]. Nature Communications, 2019, 10(1): 5127.
[12] SU X, LUO Y, TIAN Z, et al. Ctenophore-inspired Hydrogels for Efficient and Repeatable Underwater Specific Adhesion to Biotic Surfaces [J]. Materials Horizons, 2020, 7(10): 2651-2661.
[13] ZHAO Y, WU Y, WANG L, et al. Bio-inspired Reversible Underwater Adhesive [J]. Nature Communications, 2017, 8(1): 2218.
[14] LIU X, ZHANG Q, DUAN L, et al. Tough Adhesion of Nucleobase‐Tackifed Gels in Diverse Solvents [J]. Advanced Functional Materials, 2019, 29(17): 1900450.
[15] DOMPE M, CEDANO-SERRANO F J, HECKERT O, et al. Thermoresponsive Complex Coacervate-Based Underwater Adhesive [J]. Advanced Materials, 2019, 31(21): 1808179.
[16] AHMED J, GUO H, YAMAMOTO T, et al. Sliding Friction of Zwitterionic Hydrogel and Its Electrostatic Origin [J]. Macromolecules, 2014, 47(9): 3101-3107.
[17] WANG Y, HENSEL R. Bioinspired Underwater Adhesion to Rough Substrates by Cavity Collapse of Cupped Microstructures [J]. Advanced Functional Materials, 2021, 31(31): 2101787.
[18] XU L, GAO S, GUO Q, et al. A Solvent-Exchange Strategy to Regulate Noncovalent Interactions for Strong and Antiswelling Hydrogels [J]. Advanced Materials, 2020, 32(52): 2004579.
[19] XU J, JIN R, REN X, et al. Cartilage-inspired hydrogel strain sensors with ultrahigh toughness, good self-recovery and stable anti-swelling properties [J]. Journal of Materials Chemistry A, 2019, 7(44): 25441-254418.
[20] LUM K, CHANDLER D, WEEKS J D. Hydrophobicity at Small and Large Length Scales [J]. The Journal of Physical Chemistry B, 1999, 103(22): 4570-4577.
[21] WALLQVIST A, BERNE B J. Molecular Dynamics Study of the Dependence of Water Solvation Free Energy on Solute Curvature and Surface Area [J]. The Journal of Physical Chemistry, 1995, 99(9): 2885-2892.
[22] WANG Y, YAO X, WU S, et al. Bioinspired Solid Organogel Materials with a Regenerable Sacrificial Alkane Surface Layer [J]. Advanced Materials, 2017, 29(26): 1700865.
[23] LIU X, ZHANG Q, GAO G. Solvent-Resistant and Nonswellable Hydrogel Conductor toward Mechanical Perception in Diverse Liquid Media [J]. ACS Nano, 2020, 14(10): 13709-13717.
[24] 陆晨律, 王利平, 孟航飞, 等. 过冷水-壁面接触面积对冰成核行为影响实验研究[J/OL]. 上海交通大学学报, 2024, 58(3): 285-294.
[25] DOOD M J A D, KALKMAN J, STROHHöFER C, et al. Hidden Transition in the “Unfreezable Water” Region of the PVP−Water System [J]. The Journal of Physical Chemistry, 2003, 107: 5906-5913.
[26] SMYTH G, QUINN F X, MCBRIERTY V J. Water in Hydrogels: A Study of Water in Poly(hydroxyethyl methacrylate) [J]. Macromolecules, 1988, 21(11): 3198-3204.
[27] CERVENY S, COLMENERO J, ALEGRíA A. Dielectric Investigation of the Low-Temperature Water Dynamics in the Poly(vinyl methyl ether)/H2O System [J]. Macromolecules, 2005, 38(16): 7056-7063.
[28] JIAO Q, CAO L, ZHAO Z, et al. Zwitterionic Hydrogel with High Transparency, Ultrastretchability, and Remarkable Freezing Resistance for Wearable Strain Sensors [J]. Biomacromolecules, 2021, 22(3): 1220-1230.
[29] REN Y, GUO J, LIU Z, et al. Ionic Liquid–based Click-ionogels [J]. Science Advances, 2019, 5(8): eaax0648.
[30] GUO M, YAN J, YANG X, et al. A Transparent Glycerol-hydrogel with Stimuli-responsive Actuation Induced Unexpectedly at Subzero Temperatures [J]. Journal of Materials Chemistry A, 2021, 9(12): 7935-7945.
[31] HAN S, LIU C, LIN X, et al. Dual Conductive Network Hydrogel for a Highly Conductive, Self-Healing, Anti-Freezing, and Non-Drying Strain Sensor [J]. ACS Applied Polymer Materials, 2020, 2(2): 996-1005.
[32] GUN'KO V M, SAVINA I N, MIKHALOVSKY S A-O. Properties of Water Bound in Hydrogels. [J]. Gels, 2017, 3(4): 37.
[33] MO F, LIANG G, MENG Q, et al. A Flexible Rechargeable Aqueous Zinc Manganese-dioxide Battery Working at −20°C [J]. Energy & Environmental Science, 2019, 12(2): 706-715.
[34] LI G, HUANG K, DENG J, et al. Highly Conducting and Stretchable Double-Network Hydrogel for Soft Bioelectronics [J]. Advanced Materials, 2022, 34(15): 2200261.
[35] CHEN C, WANG Y, MENG T, et al. Electrically Conductive Polyacrylamide/carbon Nanotube Hydrogel: Reinforcing Effect From Cellulose Nanofibers [J]. Cellulose, 2019, 26(16): 8843-8851.
[36] 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.
[37] TONDERA C, AKBAR T F, THOMAS A K, et al. Highly Conductive, Stretchable, and Cell-Adhesive Hydrogel by Nanoclay Doping [J]. Small, 2019, 15(27): 1901406.
[38] 向勇, 闫宗楷, 朱焱麟, 等. 材料基因组技术前沿进展[J]. 电子科技大学学报. 2016, 45(04): 634-649.
[39] 王海舟, 汪洪, 丁洪, 等. 材料的高通量制备与表征技术[J]. 科技导报. 2015, 33(10): 31-49.
[40] YOO Y-K, XUE Q, CHU Y S, et al. Identification of Amorphous Phases in The Fe–Ni–Co Ternary Alloy System Using Continuous Phase Diagram Material Chips [J]. Intermetallics, 2006, 14: 241-247.
[41] XIANG X-D. High Throughput Synthesis and Screening for Functional Materials [J]. Applied Surface Science, 2004, 223(1): 54-61.
[42] CHANG K-S, GREEN M L, SUEHLE J, et al. Combinatorial Study of Ni–Ti–Pt Ternary Metal Gate Electrodes on Hf O2 for The Advanced Gate Stack [J]. Applied Physics Letters, 2006, 89(14): 142108.
[43] CHRISTEN H M, SILLIMAN S D, HARSHAVARDHAN K S. Continuous Compositional-spread Technique Based on Pulsed-laser Deposition and Applied to The Growth of Epitaxial Films [J]. Review of Scientific Instruments, 2001, 72(6): 2673-8.
[44] POTYRAILO R A, MORRIS W G, WROCZYNSKI R J. Multifunctional Sensor System for High-throughput Primary, Secondary, and Tertiary Screening of Combinatorial Materials [J]. Review of Scientific Instruments, 2004, 75(6): 2177-2186.
[45] TSUI F, HE L. Techniques for Combinatorial Molecular Beam Epitaxy [J]. Review of Scientific Instruments, 2005, 76(6): 062206.
[46] MCDOWELL M G, HILL I G. Rapid Thermal Conductivity Measurements for Combinatorial Thin Films [J]. Review of Scientific Instruments, 2013, 84(5): 053906.
[47] SURAM S K, ZHOU L, BECERRA-STASIEWICZ N, et al. Combinatorial Thin Film Composition Mapping Using Three Dimensional Deposition Profiles [J]. Review of Scientific Instruments, 2015, 86(3): 033904.
[48] LIN Z, TU S, XU J, et al. Phase Diagrams on Composition-spread FeyTe1−xSex films [J]. Science Bulletin, 2022, 67(14): 1443-1449.
[49] ZHAO J-C, ZHENG X, CAHILL D G. High-throughput Measurements of Materials Properties [J]. Journal of Management, 2011, 63(3): 40-44.
[50] LIU X-N, SHEN Y, YANG R, et al. Inkjet Printing Assisted Synthesis of Multicomponent Mesoporous Metal Oxides for Ultrafast Catalyst Exploration [J]. Nano Letters. 2012, 12 11: 5733-5739.
[51] GREGOIRE J M, MCCLUSKEY P J, DALE D, et al. Combining Combinatorial Nanocalorimetry and X-ray Diffraction Techniques to Study The Effects of Composition and Quench Rate on Au–Cu–Si Metallic Glasses [J]. Scripta Materialia, 2012, 66(3-4): 178-181.
[52] LEE D, SIM G-D, XIAO K, et al. Scanning AC nanocalorimetry Study of Zr/B Reactive Multilayers [J]. Journal of Applied Physics, 2013, 114(21): 214902.
[53] FLEISCHAUER M D, TOPPLE J M, DAHN J R. Combinatorial Investigations of Si-M  (  M  = Cr + Ni , Fe , Mn )  Thin Film Negative Electrode Materials [J]. Electrochemical and Solid-State Letters, 2005, 8(2): 137.
[54] REEVES W H, SKRYABIN D V, BIANCALANA F, et al. Transformation and Control of Ultra-short Pulses in Dispersion-Engineered Photonic Crystal Fibres [J]. Nature, 2003, 424(6948): 511-515.
[55] FUJIMOTO K, KATO T, ITO S, et al. Development and Application of Combinatorial Electrostatic Atomization System “M-ist Combi”: High-throughput Preparation of Electrode Materials [J]. Solid State Ionics, 2006, 177(26): 2639-2642.
[56] MCCLUSKEY P J, VLASSAK J J. Glass Transition and Crystallization of Amorphous Ni–Ti–Zr Thin Films by Combinatorial Nano-calorimetry [J]. Scripta Materialia, 2011, 64(3): 264-267.
[57] MCCLUSKEY P J, VLASSAK J J. Combinatorial Nanocalorimetry [J]. Journal of Materials Research, 2010, 25(11): 2086-2100.
[58] XIANG X D, SUN X, BRICEñO G, et al. A Combinatorial Approach to Materials Discovery [J]. Science, 1995, 268(5218): 1738-1740.
[59] CHANG H, GAO C, TAKEUCHI I, et al. Combinatorial Synthesis and High Throughput Evaluation of Ferroelectric/Dielectric Thin-film Libraries for Microwave Applications [J]. Applied Physics Letters, 1998, 72(17): 2185-2187.
[60] COOPER J S, ZHANG G, MCGINN P J. Plasma Sputtering System for Deposition of Thin Film Combinatorial Libraries [J]. Review of Scientific Instruments, 2005, 76(6): 062221.
[61] ZHAO J-C, XU Y, HARTMANN U. Measurement of an Iso-Curie Temperature Line of a Co, Cr, Mo Solid Solution by Magnetic Force Microscopy Imaging on a Diffusion Multiple [J]. Advanced Engineering Materials, 2013, 15(5): 321-324.
[62] GOLL D, LOEFFLER R, HERBST J, et al. Novel Permanent Magnets by High-Throughput Experiments [J]. The Journal of Operations Management, 2015, 67(6): 1336-1343.
[63] SPRINGER H, RAABE D. Rapid Alloy Prototyping: Compositional and Thermo-mechanical High Throughput Bulk Combinatorial Design of Structural Materials Based on The Example of 30Mn–1.2C–xAl Triplex Steels, Acta Materialia [J]. Science, 2012, 60(12): 4950-4959.
[64] CHEN L, BAO J, GAO C, et al. Combinatorial Synthesis of Insoluble Oxide Library from Ultrafine/nano Particle Suspension Using a Drop-on-demand Inkjet Delivery System [J]. Journal of Combinatorial Chemistry, 2004, 6(5): 699-702.
[65] DING Y, TANG H, ZHANG C, et al. High‐Throughput Screening of Self‐Healable Polysulfobetaine Hydrogels and their Applications in Flexible Electronics [J]. Advanced Functional Materials, 2021, 31(18): 2100489.
[66] CHEN Z, LU D, CAO J, et al. Development of High-throughput Wet-Chemical Synthesis Techniques for Material Research [J]. Materials Genome Engineering Advances, 2023, 1(1): e5.
[67] 高光辉, 姜海成, 高阳, 等. 高强度疏水缔合水凝胶的研究进展[J]. 长春工业大学学报. 2019, 40(01): 8-13+105.
[68] HAN L, LIU K, WANG M, et al. Mussel-Inspired Adhesive and Conductive Hydrogel with Long-Lasting Moisture and Extreme Temperature Tolerance [J]. Advanced Functional Materials, 2018, 28(3): 1704195.
[69] YU Y, YUK H, PARADA G A, et al. Multifunctional “Hydrogel Skins” on Diverse Polymers with Arbitrary Shapes [J]. Advanced Materials. 2019, 31(7): 1807101.
[70] YANG G, ZHU K, GUO W, et al. Adhesive and Hydrophobic Bilayer Hydrogel Enabled On-Skin Biosensors for High-Fidelity Classification of Human Emotion [J]. Advanced Functional Materials, 2022, 32(29): 2200457.
[71] PEI X, ZHANG H, ZHOU Y, et al. Stretchable, Self-healing and Tissue-adhesive Zwitterionic Hydrogels as Strain Sensors for Wireless Monitoring of Organ Motions [J]. Materials Horizons, 2020, 7(7): 1872-1882.
[72] HE S, SUN X, QIN Z, et al. Non-Swelling and Anti-Fouling MXene Nanocomposite Hydrogels for Underwater Strain Sensing [J]. Advanced Materials Technologies, 2022, 7(7): 2101343.
[73] GUO H, NAKAJIMA T, HOURDET D, et al. Hydrophobic Hydrogels with Fruit-Like Structure and Functions [J]. Advanced Materials, 2019, 31(25): 1900702.
[74] WEI Y, XIANG L, OU H, et al. MXene-Based Conductive Organohydrogels with Long-Term Environmental Stability and Multifunctionality [J]. Advanced Functional Materials, 2020, 30(48): 2005135.
[75] LIU X, ZHANG Q, GAO G. DNA-inspired Anti-freezing Wet-adhesion and Tough Hydrogel for Sweaty Skin Sensor [J]. Chemical Engineering Journal, 2020, 394: 124898.
[76] BALAVIGNESWARAN C K, JAISWAL V, VENKATESAN R, et al. Mussel-Inspired Adhesive Hydrogels Based on Laponite-Confined Dopamine Polymerization as a Transdermal Patch [J]. Biomacromolecules, 2023, 24(2): 724-38.
[77] LIAO M, WAN P, WEN J, et al. Wearable, Healable, and Adhesive Epidermal Sensors Assembled from Mussel-Inspired Conductive Hybrid Hydrogel Framework [J]. Advanced Functional Materials, 2017, 27(48): 1703852.
[78] PENG Q, CHEN J, WANG T, et al. Recent Advances in Designing Conductive Hydrogels for Flexible Electronics [J]. InfoMat, 2020, 2(5): 843-865.
[79] ZHENG S Y, MAO S, YUAN J, et al. Molecularly Engineered Zwitterionic Hydrogels with High Toughness and Self-Healing Capacity for Soft Electronics Applications [J]. Chemistry of Materials, 2021, 33(21): 8418-8429.
[80] ZHENG G, GAO W, LI X, et al. A κ-Carrageenan-Containing Organohydrogel with Adjustable Transmittance for an Antifreezing, Nondrying, and Solvent-Resistant Strain Sensor [J]. Biomacromolecules, 2022, 23(11): 4872-4882.
[81] ZHANG Y, XU Z, YUAN Y, et al. Flexible Antiswelling Photothermal-Therapy MXene Hydrogel-Based Epidermal Sensor for Intelligent Human–Machine Interfacing [J]. Advanced Functional Materials, 2023, 33(21): 2300299.
[82] NIE Y, YUE D, XIAO W, et al. Anti-freezing and Self-healing Nanocomposite Hydrogels Based on Poly(vinyl alcohol) for Highly Sensitive and Durable Flexible Sensors [J]. Chemical Engineering Journal, 2022, 436.
[83] WEN J, TANG J, NING H, et al. Multifunctional Ionic Skin with Sensing, UV-Filtering, Water-Retaining, and Anti-Freezing Capabilities [J]. Advanced Functional Materials, 2021, 31(21): 2011176.
[84] ZHANG X-F, MA X, HOU T, et al. Inorganic Salts Induce Thermally Reversible and Anti-Freezing Cellulose Hydrogels [J]. Angewandte Chemie International Edition, 2019, 58(22): 7366-7370.
[85] QUAN Q, FAN C, PAN N, et al. Tough and Stretchable Phenolic-Reinforced Double Network Deep Eutectic Solvent gels for Multifunctional Sensors with Environmental Adaptability [J]. Advanced Functional Materials, 2023, 33(36): 2303381.
[86] HUANG H, SHEN J, WAN S, et al. Wet-Adhesive Multifunctional Hydrogel with Anti-swelling and a Skin-Seamless Interface for Underwater Electrophysiological Monitoring and Communication [J]. ACS Applied Materials & Interfaces, 2023, 15(9): 11549-11562.
[87] WANG S, LIU J, WANG L, et al. Underwater Adhesion and Anti-Swelling Hydrogels [J]. Advanced Materials Technologies, 2023, 8(6): 2201477.
[88] ZHAO Y, GAN D, WANG L, et al. Ultra-Stretchable, Adhesive, and Anti-Swelling Ionogel Based on Fluorine-Rich Ionic Liquid for Underwater Reliable Sensor [J]. Advanced Materials Technologies, 2023, 8(7): 2201566.
[89] YANG Y, YANG Y, CAO Y, et al. Anti-freezing, Resilient and Tough Hydrogels for Sensitive and Large-range Strain and Pressure Sensors [J]. Chemical Engineering Journal, 2021, 403: 126431.
[90] LIU J, CHEN Z, CHEN Y, et al. Ionic Conductive Organohydrogels with Dynamic Pattern Behavior and Multi-Environmental Stability [J]. Advanced Functional Materials, 2021, 31(24): 2101464.
[91] CASADESúS J M, AGUIRRE F, CARRERA A, et al. Diving-related Fatalities: Multidisciplinary, Experience-based Investigation [J]. Forensic Science, Medicine and Pathology, 2019, 15(2): 224-232.