Abstract
Conductive hydrogels have garnered wide interest for various promising applications, such as wearable devices, electronic skins, and intelligent robots. However, these hydrogels still suffer from weak mechanical properties, poor environmental stability, and low sensitivity. Here, we report a conductive organohydrogel that is easily synthesized by a one-step acrylamide polymerization in the presence of cellulose nanofiber (CNF)-templated carbon nanotube (CNT) hybrids and glycerol-water binary solvent. The uniformly dispersed CNF/CNT nanohybrids act as a reinforced and conductive skeleton, which synergistically endows the organohydrogel with excellent tensile strength (≈ 119.2 kPa) and high electronic conductivity (≈ 2.7 mS cm−1). Moreover, the synergy of glycerol-water solvent network and polyacrylamide (PAAm) polymer matrix provides an ultra-stretchability (up to 1343%) and skin-like modulus (≈ 17.7 kPa), which can well match the dynamic human–machine interface. Furthermore, the organohydrogels exhibit excellent flexibility under an extreme temperature (< − 24 °C) and maintain the long-term water-retention capability in an open environment (> 10 days), owing to the glycerol-enhanced H-bonding interface interactions. Benefiting from these high performances, our organohydrogel can be employed for preparing multifunctional sensing devices, which display high sensitivity to external strains (gauge factor = 10.03) and dynamic temperature changes (temperature coefficient of resistance = − 1.081% °C−1), superior to the most reported samples. Our results pave the way for simple and practical systems that fulfill the requirements of intelligent electronic devices.
Graphical abstract
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Data availability
All data generated or analyzed during this study are included in this published article and its supplementary information files.
Code availability
Not applicable.
References
Azadi S, Peng S, Moshizi S, Asadnia M, Xu J, Park I et al (2020) Biocompatible and highly stretchable PVA/AgNWs hydrogel strain sensors for human motion detection. Adv Mater Technol 5(11):2000426. https://doi.org/10.1002/admt.202000426
Baumgartner M, Hartmann F, Drack M, Preninger D, Wirthl D, Gerstmayr R et al (2020) Resilient yet entirely degradable gelatin-based biogels for soft robots and electronics. Nat Mater 19(10):1102–1109. https://doi.org/10.1038/s41563-020-0699-3
Chen Z, Yan T, Pan Z (2021) Review of flexible strain sensors based on cellulose composites for multi-faceted applications. Cellulose 28:615–645. https://doi.org/10.1007/s10570-020-03543-6
Chu Y, Sun Y, Wu W, Xiao H (2020) Dispersion properties of nanocellulose: a review. Carbohyd Polym 250:116892. https://doi.org/10.1016/j.carbpol.2020.116892
Ding Q, Xu X, Yue Y, Mei C, Huang C, Jiang S et al (2018) Nanocellulose-mediated electroconductive self-healing hydrogels with high strength, plasticity, viscoelasticity, stretchability, and biocompatibility toward multifunctional applications. ACS Appl Mater Interfaces 10:27987–28002. https://doi.org/10.1021/acsami.8b09656
Duan Z, Jiang Y, Wang S, Yuan Z, Zhao Q, Xie G et al (2019) A low-cost, facilely fabricated, and environment-friendly strain sensor based on common carbon ink and elastic core-spun yarn. ACS Sustainable Chem Eng 7:17474–17481. https://doi.org/10.1021/acssuschemeng.9b04690
Duan Z, Jiang Y, Huang Q, Wang S, Zhao Q, Zhang Y et al (2021a) Facilely constructed two-sided microstructure interfaces between electrodes and cellulose paper active layer: eco-friendly, low-cost and high-performance piezoresistive sensor. Cellulose 28:6389–6402. https://doi.org/10.1007/s10570-021-03913-8
Duan Z, Jiang Y, Huang Q, Yuan Z, Zhao Q, Wang S et al (2021b) A do-it-yourself approach to achieving a flexible pressure sensor using daily use materials. J Mater Chem C 9:13659–13667. https://doi.org/10.1039/D1TC03102C
Duan Z, Jiang Y, Huang Q, Wang S, Wang Y, Pan H et al (2021c) Paper and carbon ink enabled low-cost, eco-friendly, flexible, multifunctional pressure and humidity sensors. Smart Mater Struct 30:055012. https://doi.org/10.1088/1361-665X/abe87d/meta
Ge W, Cao S, Yang Y, Rojas O, Wang X (2020) Nanocellulose/LiCl systems enable conductive and stretchable electrolyte hydrogels with tolerance to dehydration and extreme cold conditions. Chem Eng J 408:127306. https://doi.org/10.1016/j.cej.2020.127306
Gu J, Huang J, Chen G, Hou L, Zhang J, Zhang X et al (2020) Multifunctional poly(vinyl alcohol) nanocomposite organohydrogel for flexible strain and temperature sensor. ACS Appl Mater Interfaces 12(36):40815–40827. https://doi.org/10.1021/acsami.0c12176
Hamedi M, Hajian A, Fall A, Håkansson K, Salajkova M, Lundell F et al (2014) Highly conducting, strong nanocomposites based on nanocellulose-assisted aqueous dispersions of single-wall carbon nanotubes. ACS Nano 8(3):2467–2476. https://doi.org/10.1021/nn4060368
Han L, Lu X, Wang M, Gan D, Deng W, Wang K et al (2017) A mussel-inspired conductive, self-adhesive, and self-healable tough hydrogel as cell stimulators and implantable bioelectronics. Small 13(2):1601916. https://doi.org/10.1002/smll.201601916
Han J, Wang H, Yue Y, Mei C, Chen J, Huang C et al (2019a) A self-healable and highly flexible supercapacitor integrated by dynamically cross-linked electro-conductive hydrogels based on nanocellulose-templated carbon nanotubes embedded in a viscoelastic polymer network. Carbon 149:1–18. https://doi.org/10.1016/j.carbon.2019.04.029
Han J, Wang S, Zhu S, Huang C, Yue Y, Mei C et al (2019b) Electrospun core–shell nanofibrous membranes with nanocellulose-stabilized carbon nanotubes for use as high-performance flexible supercapacitor electrodes with enhanced water resistance, thermal stability, and mechanical toughness. ACS Appl Mater Interfaces 11:44624–44635. https://doi.org/10.1021/acsami.9b16458
Han J, Lu K, Yue Y, Mei C, Huang C, Wu Q et al (2019c) Nanocellulose-templated assembly of polyaniline in natural rubber-based hybrid elastomers toward flexible electronic conductors. Ind Crop Prod 128:94–107. https://doi.org/10.1016/j.indcrop.2018.11.004
Han J, Ding Q, Mei C, Wu Q, Yue Y, Xu X (2019d) An intrinsically self-healing and biocompatible electroconductive hydrogel based on nanostructured nanocellulose-polyaniline complexes embedded in a viscoelastic polymer network towards flexible conductors and electrodes. Electrochim Acta 318:660–672. https://doi.org/10.1016/j.electacta.2019.06.132
Han L, Liu K, Wang M, Wang K, Fang L, Chen H et al (2018) Mussel-inspired adhesive and conductive hydrogel with long-lasting moisture and extreme temperature tolerance. Adv Funct Mater 28(3):1704195. https://doi.org/10.1002/adfm.201704195
Jiao Y, Lu K, Lu Y, Yue Y, Xu X, Xiao H et al (2021a) Highly viscoelastic, stretchable, conductive, and self-healing strain sensors based on cellulose nanofiber-reinforced polyacrylic acid hydrogel. Cellulose 28:4295–4311. https://doi.org/10.1007/s10570-021-03782-1
Jiao Y, Lu Y, Lu K, Yue Y, Xu X, Xiao H et al (2021b) Highly stretchable and self-healing cellulose nanofiber-mediated conductive hydrogel towards strain sensing application. J Colloid Interf Sci 597:171–181. https://doi.org/10.1016/j.jcis.2021.04.001
Jing X, Mi H, Peng X, Turng L (2018) Biocompatible, self-healing, highly stretchable polyacrylic acid/reduced graphene oxide nanocomposite hydrogel sensors via mussel-inspired chemistry. Carbon 136:63–72. https://doi.org/10.1016/j.carbon.2018.04.065
Li Z, Zhang S, Chen Y, Ling H, Zhao L, Luo G et al (2020) Gelatin methacryloyl-based tactile sensors for medical wearables. Adv Funct Mater 30(49):2003601. https://doi.org/10.1002/adfm.202003601
Liao H, Guo X, Wan P, Yu G (2019) Conductive MXene nanocomposite organohydrogel for flexible, healable, low-temperature tolerant strain sensors. Adv Funct Mater 29(39):1904507. https://doi.org/10.1002/adfm.201904507
Lim H, Kim H, Qazi R, Kwon Y, Yeo W (2020) Advanced soft materials, sensor integrations, and applications of wearable flexible hybrid electronics in healthcare, energy, and environment. Adv Mater 32(15):1901924. https://doi.org/10.1002/adma.201901924
Lu Y, Yue Y, Ding Q, Mei C, Xu X, Wu Q et al (2021a) Self-recovery, fatigue-resistant, and multifunctional sensor assembled by a nanocellulose/carbon nanotube nanocomplex-mediated hydrogel. ACS Appl Mater Interfaces 13:50281–50297. https://doi.org/10.1021/acsami.1c16828
Lu Y, Han J, Ding Q, Yue Y, Xia C, Ge S et al (2021b) TEMPO-oxidized cellulose nanofibers/polyacrylamide hybrid hydrogel with intrinsic self-recovery and shape memory properties. Cellulose 28:1469–1488. https://doi.org/10.1007/s10570-020-03606-8
Lu Y, Qu X, Zhao W, Ren Y, Si W, Wang W et al (2020) Highly stretchable, elastic, and sensitive MXene-based hydrogel for flexible strain and pressure sensors. Research 2020(11):1–13. https://doi.org/10.34133/2020/2038560
Niu Y, Liu H, He R, Li Z, Xu F (2020) The new generation of soft and wearable electronics for health monitoring in varying environment: from normal to extreme conditions. Mater Today 41(6):219–242. https://doi.org/10.1016/j.mattod.2020.10.004
Niu Z, Cheng W, Cao M, Wang D, Wang Q, Han J et al (2021) Recent advances in cellulose-based flexible triboelectric nanogenerators. Nano Energy 87:106175. https://doi.org/10.1016/j.nanoen.2021.106175
Rong Q, Lei W, Chen L, Yin Y, Zhou J, Liu M (2017) Anti-freezing, conductive self-healing organohydrogels with stable strain-sensitivity at subzero temperatures. Angew Chem Int Ed 56(45):14159–14163. https://doi.org/10.1002/anie.201708614
Saeb M, Rabiee N, Seidi F, Far B, Bagherzadeh M, Lima E et al (2021) Green CoNi2S4/porphyrin decorated carbon-based nanocomposites for genetic materials detection. J Bioresour Bioprod 6:215–222. https://doi.org/10.1016/j.jobab.2021.06.001
Wang L, Wang K, Lou Z, Jiang K, Shen G (2018) Plant-based modular building blocks for “green” electronic skins. Adv Funct Mater 28(51):1804510. https://doi.org/10.1002/adfm.201804510
Wang H, Biswas S, Zhu S, Lu Y, Yue Y, Han J et al (2020) Self-healable electro-conductive hydrogels based on core-shell structured nanocellulose/carbon nanotubes hybrids for use as flexible supercapacitors. Nanomaterials 10:112. https://doi.org/10.3390/nano10010112
Wei Y, Xiang L, Ou H, Li F, Zhang Y, Qian Y et al (2020) MXene-based conductive organohydrogels with long-term environmental stability and multifunctionality. Adv Funct Mater 30(48):2005135. https://doi.org/10.1002/adfm.202005135
Wu J, Han S, Yang T, Li Z, Wu Z, Gui X et al (2018) Highly stretchable and transparent thermistor based on self-healing double network hydrogel. ACS Appl Mater Interfaces 10:19097–19105. https://doi.org/10.1021/acsami.8b03524
Wu J, Wu Z, Xu H, Wu Q, Liu C, Yang B et al (2019) An intrinsically stretchable humidity sensor based on anti-drying, self-healing and transparent organohydrogels. Mater Horiz 6:595–603. https://doi.org/10.1039/C8MH01160E
Yang X, Biswas S, Han J, Tanpichai S, Li M, Chen C et al (2020) Surface and interface engineering for nanocellulosic. Adv Mater 33:2002264. https://doi.org/10.1002/adma.202002264
Ye Y, Zhang Y, Chen Y, Han X, Jiang F (2020) Cellulose nanofibrils enhanced, strong, stretchable, freezing-tolerant ionic conductive organohydrogel for multifunctional sensors. Adv Funct Mater 30(35):2003430. https://doi.org/10.1002/adfm.202003430
Yu Y, Yuk H, Parada G, Wu Y, Liu X, Nabzdyk C et al (2019) Multifunctional “hydrogel skins” on diverse polymers with arbitrary shapes. Adv Mater 31(7):1807101. https://doi.org/10.1002/adma.201807101
Yuk H, Lu B, Zhao X (2018) Hydrogel bioelectronics. Chem Soc Rev 48(6):1642–1667. https://doi.org/10.1039/C8CS00595H
Zeng X, Deng L, Yao Y, Sun R, Xu J, Wong C (2016) Flexible dielectric papers based on biodegradable cellulose nanofibers and carbon nanotubes for dielectric energy storage. J Mater Chem C 4:6037–6044. https://doi.org/10.1039/C6TC01501H
Zheng C, Lu K, Lu Y, Zhu S, Yue Y, Xu X et al (2020) A stretchable, self-healing conductive hydrogels based on nanocellulose supported graphene towards wearable monitoring of human motion. Carbohydr Polym 250:116905. https://doi.org/10.1016/j.carbpol.2020.116905
Zhong M, Liu Y, Xie X (2015) Self-healable, super tough graphene oxide-poly(acrylic acid) nanocomposite hydrogels facilitated by dual cross-linking effects through dynamic ionic interactions. J Mater Chem B 3:4001–4008. https://doi.org/10.1039/C5TB00075K
Zhu P, Kuang Y, Wei Y, Li F, Ou H, Jiang F (2021) Electrostatic self-assembly enabled flexible paper-based humidity sensor with high sensitivity and superior durability. Chem Eng J 404:127105. https://doi.org/10.1016/j.cej.2020.127105
Acknowledgments
The authors acknowledge the financial support of the National Key Research and Development Program of China (2018YFC1902102), State Key Laboratory of Pulp and Paper Engineering at South China University of Technology (2020ZD02), and the Guangdong Basic and Applied Basic Research Project General Program (2021A1515010538). L.X. acknowledges the support of the Program of “Bai Bu Ti Climbing Plan in 2020” at South China University of Technology (j2tw202004041). Informed consent was obtained from all participants for the experiments involving wearable sensors.
Funding
The National Key Research and Development Program of China (2018YFC1902102); The Program of State Key Laboratory of Pulp and Paper Engineering at South China University of Technology (2020ZD02); The General Program of Guangdong Basic and Applied Basic Research Project (2021A1515010538); The Program of “Bai Bu Ti Climbing Plan in 2020” at South China University of Technology (j2tw202004041).
Author information
Authors and Affiliations
Contributions
YW: conceptualization, investigation, methodology, writing–original draft. YQ: methodology, formal analysis, investigation, visualization. PZ: methodology, Software. LX: data curation, resources. CL: methodology. GQ: methodology. CW: validation. YL: formal analysis. YL: formal analysis. GC: conceptualization, methodology, formal analysis, funding acquisition, writing — review and editing, supervision.
Corresponding author
Ethics declarations
Conflicts of interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Wei, Y., Qian, Y., Zhu, P. et al. Nanocellulose-templated carbon nanotube enhanced conductive organohydrogel for highly-sensitive strain and temperature sensors. Cellulose 29, 3829–3844 (2022). https://doi.org/10.1007/s10570-022-04516-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-022-04516-7