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Research Article

An injectable, self-healable, and reusable PEDOT:PSS/PVA hydrogel patch electrode for epidermal electronics

Yang Li1,2,§( ), Yuzhe Gu1,§, Sheng Qian2, Shuwen Zheng1, Yuncong Pang2, Lele Wang1, Baoguang Liu1, Shujuan Liu2( ), Qiang Zhao1,2( )
College of Electronic and Optical Engineering and College of Flexible Electronics (Future Technology), Nanjing University of Posts and Telecommunications (NJUPT), Nanjing 210023, China
State Key Laboratory of Organic Electronics and Information Displays and Jiangsu Key Laboratory for Biosensors, Institute of Advanced Materials (IAM), Nanjing University of Posts and Telecommunications (NJUPT), Nanjing 210023, China

§ Yang Li and Yuzhe Gu contributed equally to this work.

Show Author Information

Graphical Abstract

This paper introduces a conductive, injectable, and self-healing poly(3,4-ethylenedioxythiophene):polystyrene sulfonate/polyvinyl alcohol (PEDOT:PSS/PVA) hydrogel tailored for epidermal electronic components, showcasing significantly enhanced performance compared to traditional electrodes. It serves multifaceted purposes, offering applicability in diverse electrophysiological monitoring and potential substitution for commercial conductive pastes in repetitive brain–computer interface (BCI) testing.

Abstract

Injectability empowers conductive hydrogels to transcend traditional limitations, unlocking a realm of possibilities for innovative medical, wearable, and therapeutic applications that can significantly enhance patient care and quality of life. Here, we report an injectable, self-healable, and reusable hydrogel obtained by mixing the concentrated poly(3,4-ethylenedioxythiophene) doped with polystyrene sulfonate (PEDOT:PSS) suspension (~ 2 wt.% solid content), polyvinyl alcohol (PVA), and borax. Leveraging the presence of reversible borax/hydroxyl bonds and multiple hydrogen bonds, this PEDOT:PSS/PVA hydrogel exhibits notable shear-thinning behavior and self-healing capabilities, enabling it to be injected as a gel fiber from a syringe. As-prepared injectable hydrogel also demonstrates an ultra-low modulus (~ 2.5 MPa), reduced on-skin impedance (~ 45% of commercial electrodes), and high signal-to-noise ratio (SNR) (~ 15–22 dB) in recording of electrocardiography (ECG), electromyography (EMG), and electroencephalogram (EEG) signals. Furthermore, the injectable hydrogels can be remolded and reinjected as the reusable electrodes, maintaining nearly identical electrophysiological recording capabilities and brain–computer interface (BCI) performance compared to commercial wet electrodes. With their straightforward fabrication, excellent material properties and electronic performance, ease of cleaning, and remarkable reusability, our injectable PEDOT:PSS/PVA hydrogels hold promise for advancements in BCI based electronics and wearable bioelectronics.

Keywords

epidermal hydrogel electrodesreusabilityinjectabilityself-healingelectrophysiological recordingbrain–computer interface

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References

[1]

Jiang, Y.; Ji, S. B.; Sun, J.; Huang, J. P.; Li, Y. H.; Zou, G. J.; Salim, T.; Wang, C. X.; Li, W. L.; Jin, H. R. et al. A universal interface for plug-and-play assembly of stretchable devices. Nature 2023, 614, 456–462.
Crossref Google Scholar
[2]

Zhao, Y. C.; Wang, B.; Tan, J. W.; Yin, H. X.; Huang, R. Y.; Zhu, J. L.; Lin, S. Y.; Zhou, Y.; Jelinek, D.; Sun, Z. Y. et al. Soft strain-insensitive bioelectronics featuring brittle materials. Science 2022, 378, 1222–1227.
Crossref Google Scholar
[3]

Li, G.; Huang, K. X.; Deng, J.; Guo, M. X.; Cai, M. K.; Zhang, Y.; Guo, C. F. Highly conducting and stretchable double-network hydrogel for soft bioelectronics. Adv. Mater. 2022, 34, 2200261.
Crossref Google Scholar
[4]
Feng, T. X.; Ling, D.; Li, C. Y.; Zheng, W. T.; Zhang, S. C.; Li, C.; Emel’yanov, A.; Pozdnyakov, A. S.; Lu, L. J.; Mao, Y. C. Stretchable on-skin touchless screen sensor enabled by ionic hydrogel. Nano Res., in press, https://doi.org/10.1007/s12274-023-6365-8.
[5]

Li, J.; Carlos, C.; Zhou, H.; Sui, J. J.; Wang, Y. K.; Silva-Pedraza, Z.; Yang, F.; Dong, Y. T.; Zhang, Z. Y.; Hacker, T. A. et al. Stretchable piezoelectric biocrystal thin films. Nat. Commun. 2023, 14, 6562.
Crossref Google Scholar
[6]

Wang, C. Y.; Wang, H. Y.; Wang, B. H.; Miyata, H.; Wang, Y.; Nayeem, M. O. G.; Kim, J. J.; Lee, S.; Yokota, T.; Onodera, H. et al. On-skin paintable biogel for long-term high-fidelity electroencephalogram recording. Sci. Adv. 2022, 8, eabo1396.
Crossref Google Scholar
[7]

Xu, Z. Y.; Qiao, X. J.; Tao, R. Z.; Li, Y. X.; Zhao, S. J.; Cai, Y. C.; Luo, X. L. A wearable sensor based on multifunctional conductive hydrogel for simultaneous accurate pH and tyrosine monitoring in sweat. Biosens. Bioelectron. 2023, 234, 115360.
Crossref Google Scholar
[8]

Kim, M.; Um, H. K.; Choi, H.; Lee, J. S.; Kim, J.; Kim, K.; Noh, E.; Han, M.; Lee, H. W.; Choi, W. I. et al. Stretchable and biocompatible transparent electrodes for multimodal biosignal sensing from exposed skin. Adv. Electron. Mater. 2023, 9, 2300075.
Crossref Google Scholar
[9]

Bian, Z. Y.; Li, Y. H.; Sun, H. L.; Shi, M. Y.; Zheng, Y. J.; Liu, H.; Liu, C. T.; Shen, C. Y. Transparent, intrinsically stretchable cellulose nanofiber-mediated conductive hydrogel for strain and humidity sensing. Carbohydr. Polym. 2023, 301, 120300.
Crossref Google Scholar
[10]

Hsieh, J. C.; Alawieh, H.; Li, Y.; Iwane, F.; Zhao, L. R.; Anderson, R.; Abdullah, S. I.; Kevin Tang, K. W.; Wang, W. L.; Pyatnitskiy, I. et al. A highly stable electrode with low electrode-skin impedance for wearable brain–computer interface. Biosens. Bioelectron. 2022, 218, 114756.
Crossref Google Scholar
[11]

Li, M.; Li, W. J.; Guan, Q. W.; Lv, J.; Wang, Z. H.; Ding, L.; Li, C.; Saiz, E.; Hou, X. Sweat-resistant bioelectronic skin sensor. Device 2023, 1, 100006.
Crossref Google Scholar
[12]
Li, J. L.; Liu, Z. H.; Tang, Y. T.; Xian, J. B.; He, C. F.; Wu, H.; Liu, M. J.; Li, F. Y. An interfacial gel electrode patch with tunable hydrogen bond network for electromyographic sensing and discrimination. CCS Chem., in press, https://doi.org/10.31635/ccschem.023.202202564.
[13]

Yuk, H.; Wu, J. J.; Zhao, X. H. Hydrogel interfaces for merging humans and machines. Nat. Rev. Mater. 2022, 7, 935–952.
Crossref Google Scholar
[14]

Zhou, T.; Yuk, H.; Hu, F. Q.; Wu, J. J.; Tian, F. J.; Roh, H.; Shen, Z. Q.; Gu, G. Y.; Xu, J. K.; Lu, B. Y. et al. 3D printable high-performance conducting polymer hydrogel for all-hydrogel bioelectronic interfaces. Nat. Mater. 2023, 22, 895–902
Crossref Google Scholar
[15]

Hu, L. X.; Chee, P. L.; Sugiarto, S.; Yu, Y.; Shi, C. Q.; Yan, R.; Yao, Z. Q.; Shi, X. W.; Zhi, J. C.; Kai, D. et al. Hydrogel-based flexible electronics. Adv. Mater. 2023, 35, 2205326.
Crossref Google Scholar
[16]

Tang, X.; Shen, H.; Zhao, S. Y.; Li, N.; Liu, J. Flexible brain–computer interfaces. Nat. Electron. 2023, 6, 109–118.
Crossref Google Scholar
[17]

Vashahi, F.; Martinez, M. R.; Dashtimoghadam, E.; Fahimipour, F.; Keith, A. N.; Bersenev, E. A.; Ivanov, D. A.; Zhulina, E. B.; Popryadukhin, P.; Matyjaszewski, K. et al. Injectable bottlebrush hydrogels with tissue-mimetic mechanical properties. Sci. Adv. 2022, 8, eabm2469.
Crossref Google Scholar
[18]

Yu, C. J.; Yue, Z. W.; Zhang, H.; Shi, M. Y.; Yao, M. M.; Yu, Q. Y.; Liu, M.; Guo, B. Y.; Zhang, H. T.; Tian, L. Q. et al. Ultra-histocompatible and electrophysiological-adapted PEDOT-based hydrogels designed for cardiac repair. Adv. Funct. Mater. 2023, 33, 2211023.
Crossref Google Scholar
[19]

Hui, Y.; Yao, Y.; Qian, Q. L.; Luo, J. H.; Chen, H. H.; Qiao, Z.; Yu, Y. T.; Tao, L.; Zhou, N. J. Three-dimensional printing of soft hydrogel electronics. Nat. Electron. 2022, 5, 893–903.
Crossref Google Scholar
[20]

Chen, K.; Wu, Z. H.; Liu, Y. T.; Yuan, Y.; Liu, C. S. Injectable double-crosslinked adhesive hydrogels with high mechanical resilience and effective energy dissipation for joint wound treatment. Adv. Funct. Mater. 2022, 32, 2109687.
Crossref Google Scholar
[21]
Li, Y.; Ding, P. P.; Gu, Y. Z.; Qian, S.; Pang, Y. C.; Wang, L. L.; Feng, J. Y.; Liu, B. G.; Wan, Q.; Li, P. et al. Self-healable gels in electrochemical energy storage devices. Nano Res., in press, https://doi.org/10.1007/s12274-023-6063-6.
[22]

Donahue, M. J.; Sanchez-Sanchez, A.; Inal, S.; Qu, J.; Owens, R. M.; Mecerreyes, D.; Malliaras, G. G.; Martin, D. C. Tailoring PEDOT properties for applications in bioelectronics. Mater. Sci. Eng. R: Rep. 2020, 140, 100546.
Crossref Google Scholar
[23]

Zhang, S. M.; Li, Y.; Tomasello, G.; Anthonisen, M.; Li, X. D.; Mazzeo, M.; Genco, A.; Grutter, P.; Cicoira, F. Tuning the electromechanical properties of PEDOT:PSS films for stretchable transistors and pressure sensors. Adv. Electron. Mater. 2019, 5, 1900191.
Crossref Google Scholar
[24]

Li, Y.; Zhang, S. M.; Li, X. D.; Unnava, V. R. N.; Cicoira, F. Highly stretchable PEDOT:PSS organic electrochemical transistors achieved via polyethylene glycol addition. Flex. Print. Electron. 2019, 4, 044004.
Crossref Google Scholar
[25]

Chiong, J. A.; Tran, H.; Lin, Y. J.; Zheng, Y.; Bao, Z. N. Integrating emerging polymer chemistries for the advancement of recyclable, biodegradable, and biocompatible electronics. Adv. Sci. 2021, 8, 2101233.
Crossref Google Scholar
[26]

Li, Y.; Li, X. D.; Zhang, S. M.; Liu, L.; Hamad, N.; Bobbara, S. R.; Pasini, D.; Cicoira, F. Autonomic self-healing of PEDOT:PSS achieved via polyethylene glycol addition. Adv. Funct. Mater. 2020, 30, 2002853.
Crossref Google Scholar
[27]

Li, Y.; Zhang, S. M.; Hamad, N.; Kim, K.; Liu, L.; Lerond, M.; Cicoira, F. Tailoring the self-healing properties of conducting polymer films. Macromol. Biosci. 2020, 20, 2000146.
Crossref Google Scholar
[28]

Li, Y.; Zhou, X.; Sarkar, B.; Gagnon-Lafrenais, N.; Cicoira, F. Recent progress on self-healable conducting polymers. Adv. Mater. 2022, 34, 2108932.
Crossref Google Scholar
[29]

Yu, C. J.; Yao, F. L.; Li, J. J. Rational design of injectable conducting polymer-based hydrogels for tissue engineering. Acta Biomater. 2022, 139, 4–21.
Crossref Google Scholar
[30]

Xu, Y.; Patsis, P. A.; Hauser, S.; Voigt, D.; Rothe, R.; Günther, M.; Cui, M. Y.; Yang, X. G.; Wieduwild, R.; Eckert, K. et al. Cytocompatible, injectable, and electroconductive soft adhesives with hybrid covalent/noncovalent dynamic network. Adv. Sci. 2019, 6, 1802077.
Crossref Google Scholar
[31]

Zhang, S. M.; Chen, Y. H.; Liu, H.; Wang, Z. T.; Ling, H. N.; Wang, C. S.; Ni, J. H.; Çelebi-Saltik, B.; Wang, X. C.; Meng, X. et al. Room-temperature-formed PEDOT:PSS hydrogels enable injectable, soft, and healable organic bioelectronics. Adv. Mater. 2020, 32, 1904752.
Crossref Google Scholar
[32]

Huang, X. X.; Chen, C. W.; Ma, X. H.; Zhu, T. S.; Ma, W. C.; Jin, Q.; Du, R. C.; Cai, Y. F.; Zhang, M. H.; Kong, D. S. et al. In situ forming dual-conductive hydrogels enable conformal, self-adhesive and antibacterial epidermal electrodes. Adv. Funct. Mater. 2023, 33, 2302846.
Crossref Google Scholar
[33]

Shi, Y. K.; Wu, B. H.; Sun, S. T.; Wu, P. Y. Aqueous spinning of robust, self-healable, and crack-resistant hydrogel microfibers enabled by hydrogen bond nanoconfinement. Nat. Commun. 2023, 14, 1370.
Crossref Google Scholar
[34]

Niu, W. W.; Tian, Q.; Liu, Z. Y.; Liu, X. K. Solvent-free and skin-like supramolecular ion-conductive elastomers with versatile processability for multifunctional ionic tattoos and on-skin bioelectronics. Adv. Mater. 2023, 35, 2304157.
Crossref Google Scholar
[35]

Tan, P.; Wang, H. F.; Xiao, F. R.; Lu, X.; Shang, W. H.; Deng, X. B.; Song, H. F.; Xu, Z. Y.; Cao, J. F.; Gan, T. S. et al. Solution-processable, soft, self-adhesive, and conductive polymer composites for soft electronics. Nat. Commun. 2022, 13, 358.
Crossref Google Scholar
[36]

Ma, H. D.; Hou, J. D.; Xiao, X.; Wan, R. T.; Ge, G.; Zheng, W. Q.; Chen, C.; Cao, J.; Wang, J. Y.; Liu, C. et al. Self-healing electrical bioadhesive interface for electrophysiology recording. J. Colloid Interface Sci. 2024, 654, 639–648.
Crossref Google Scholar
[37]

Lu, B. Y.; Yuk, H.; Lin, S. T.; Jian, N. N.; Qu, K.; Xu, J. K.; Zhao, X. H. Pure PEDOT:PSS hydrogels. Nat. Commun. 2019, 10, 1043.
Crossref Google Scholar
[38]

Jing, X.; Li, H.; Mi, H. Y.; Liu, Y. J.; Feng, P. Y.; Tan, Y. M.; Turng, L. S. Highly transparent, stretchable, and rapid self-healing polyvinyl alcohol/cellulose nanofibril hydrogel sensors for sensitive pressure sensing and human motion detection. Sens. Actuators B: Chem. 2019, 295, 159–167.
Crossref Google Scholar
[39]

Shin, M.; Shin, S. H.; Lee, M.; Kim, H. J.; Jeong, J. H.; Choi, Y. H.; Oh, D. X.; Park, J.; Jeon, H.; Eom, Y. Rheological criteria for distinguishing self-healing and non-self-healing hydrogels. Polymer 2021, 229, 123969.
Crossref Google Scholar
[40]

Correa, S.; Grosskopf, A. K.; Lopez Hernandez, H.; Chan, D.; Yu, A. C.; Stapleton, L. M.; Appel, E. A. Translational applications of hydrogels. Chem. Rev. 2021, 121, 11385–11457.
Crossref Google Scholar
[41]

Lu, B. L.; Lin, F. C.; Jiang, X.; Cheng, J. J.; Lu, Q. L.; Song, J. B.; Chen, C.; Huang, B. One-pot assembly of microfibrillated cellulose reinforced PVA-borax hydrogels with self-healing and pH-responsive properties. ACS Sustain. Chem. Eng. 2017, 5, 948–956.
Crossref Google Scholar
[42]

Li, G. L.; Liu, Y.; Chen, Y. W.; Xia, Y. H.; Qi, X. M.; Wan, X.; Jin, Y.; Liu, J.; He, Q. G.; Li, K. H. et al. Robust, self-adhesive, and low-contact impedance polyvinyl alcohol/polyacrylamide dual-network hydrogel semidry electrode for biopotential signal acquisition. SmartMat 2023, 4, e1173
Crossref Google Scholar
[43]

Ding, Y. F.; Shi, Y. F.; Yu, D.; Wang, W. All-in-one sandwich-like PVA/PEDOT:PSS/WPU electrodes with low impedance and high stretchability for ECG monitoring. Colloids Surf. A: Physicochem. Eng. Aspects 2023, 675, 132060.
Crossref Google Scholar
[44]

McGlynn, E.; Nabaei, V.; Ren, E.; Galeote-Checa, G.; Das, R.; Curia, G.; Heidari, H. The future of neuroscience: Flexible and wireless implantable neural electronics. Adv. Sci. 2021, 8, 2002693.
Crossref Google Scholar
[45]

Hsieh, J. C.; Li, Y.; Wang, H. Q.; Perz, M.; Tang, Q.; Tang, K. W. K.; Pyatnitskiy, I.; Reyes, R.; Ding, H.; Wang, H. L. Design of hydrogel-based wearable EEG electrodes for medical applications. J. Mater. Chem. B 2022, 10, 7260–7280.
Crossref Google Scholar
[46]

Shen, G. C.; Zheng, K. Y.; Jiang, C. P.; Shao, S. H.; Zhao, N.; Liu, J. Q. A gelatin-based hydrogel electrode with high moisturizing ability for wearable EEG recording. IEEE Sens. J. 2023, 23, 25689–25697.
Crossref Google Scholar
[47]

Xue, H. L.; Wang, D. Y.; Jin, M. Y.; Gao, H. B.; Wang, X. H.; Xia, L.; Li, D. A.; Sun, K.; Wang, H. N.; Dong, X. F. et al. Hydrogel electrodes with conductive and substrate-adhesive layers for noninvasive long-term EEG acquisition. Microsyst. Nanoeng. 2023, 9, 79.
Crossref Google Scholar
[48]

Shen, G. C.; Gao, K. P.; Zhao, N.; Wang, Z. Z.; Jiang, C. P.; Liu, J. Q. A fully flexible hydrogel electrode for daily EEG monitoring. IEEE Sens. J. 2022, 22, 12522–12529.
Crossref Google Scholar
[49]

Shen, G. C.; Gao, K. P.; Zhao, N.; Yi, Z. R.; Jiang, C. P.; Yang, B.; Liu, J. Q. A novel flexible hydrogel electrode with a strong moisturizing ability for long-term EEG recording. J. Neural Eng. 2021, 18, 066047.
Crossref Google Scholar
[50]

Li, G. L.; Liu, Y.; Chen, Y. W.; Li, M. Z.; Song, J.; Li, K. H.; Zhang, Y. M.; Hu, L.; Qi, X. M.; Wan, X. et al. Polyvinyl alcohol/polyacrylamide double-network hydrogel-based semi-dry electrodes for robust electroencephalography recording at hairy scalp for noninvasive brain-computer interfaces. J. Neural Eng. 2023, 20, 026017.
Crossref Google Scholar
[51]

Timosina, V.; Cole, T.; Lu, H. D.; Shu, J.; Zhou, X. B.; Zhang, C. C.; Guo, J. H.; Kavehei, O.; Tang, S. Y. A non-newtonian liquid metal enabled enhanced electrography. Biosens. Bioelectron. 2023, 235, 115414.
Crossref Google Scholar
[52]

Zhou, X.; Rajeev, A.; Subramanian, A.; Li, Y.; Rossetti, N.; Natale, G.; Lodygensky, G. A.; Cicoira, F. Self-healing, stretchable, and highly adhesive hydrogels for epidermal patch electrodes. Acta Biomater. 2022, 139, 296–306.
Crossref Google Scholar
[53]

Yang, G. G.; Zhu, K. H.; Guo, W.; Wu, D. R.; Quan, X. L.; Huang, X.; Liu, S. Y.; Li, Y. Y.; Fang, H.; Qiu, Y. Q. et al. Adhesive and hydrophobic bilayer hydrogel enabled on-skin biosensors for high-fidelity classification of human emotion. Adv. Funct. Mater. 2022, 32, 2200457.
Crossref Google Scholar
[54]

Du, X. J.; Yang, L. Y.; Liu, N. Recent progress on poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) bioelectrodes. Small Sci. 2023, 3, 2300008.
Crossref Google Scholar
[55]

Jastrzebska-Perfect, P.; Chowdhury, S.; Spyropoulos, G. D.; Zhao, Z. F.; Cea, C.; Gelinas, J. N.; Khodagholy, D. Translational neuroelectronics. Adv. Funct. Mater. 2020, 30, 1909165.
Crossref Google Scholar
Nano Research
Volume 17 Issue 6,
June 2024
Pages 5479-5490
DOI: 10.1007/s12274-024-6515-7
Cite this article:
Li Y, Gu Y, Qian S, et al. An injectable, self-healable, and reusable PEDOT:PSS/PVA hydrogel patch electrode for epidermal electronics. Nano Research, 2024, 17(6): 5479-5490. https://doi.org/10.1007/s12274-024-6515-7
Topics:
ElectrophysiologyGelsMedical applicationsOrganic semiconductor materialsSignal detectionWearable technology

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Received: 14 December 2023
Revised: 25 January 2024
Accepted: 25 January 2024
Published: 22 March 2024
© Tsinghua University Press 2024
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