Interfacial Modulation of Polydopamine–Reduced Graphene Oxide for Achieving Highly Conductive and Strong Graphene/Cotton Composite Yarn Toward Smart Wearable Devices

Abstract

Graphene composite yarns have demonstrated significant potential in the development of multifunctional wearable electronics, showcasing exceptional conductivity, mechanical properties, flexibility, and lightweight design. However, their performance is limited by the weak interfacial interaction between the fibers and graphene. Herein, a polydopamine–reduced graphene oxide (PDA–RGO) interfacial modulation strategy is proposed to prepare graphene-coated cotton yarns with high electrical conductivity and strength. PDA–RGO serves as an interfacial bonding molecule that interacts with the cotton yarn (CY) substrate to establish a hydrogen interface, while interconnecting with highly conductive graphene through π–π interactions. The developed interface-designed graphene-coated yarn demonstrates an impressive average electrical conductivity of (856.27 ± 7.02) S/m (i.e., average resistance of (57.57 ± 5.35) Ω). Simultaneously, the obtained conductive yarn demonstrates an exceptional average tensile strength of (172.03 ± 8.03) MPa, surpassing that of primitive CY by approximately 1.59 times. The conductive yarns can be further used as low-voltage flexible wearable heaters and high-sensitivity pressure sensors, thus showcasing their remarkable potential for high-performance and multifunctional wearable devices in real-world applications.

Graphical Abstract

References

[1.] GongS, LuY, YinJ, LevinA, ChengW. Materials-driven soft wearable bioelectronics for connected healthcare. Chem Rev, 2024, 124: 455

[2.] QuS, LiuJ, HuJ, SunL, XuW. Flexible DPPT-TT/PEO fiber-exploiting electro-optical synaptic transistor for artificial withdrawal reflex Arc. Adv Fiber Mater, 2024, 6: 401

[3.] KimY, ChortosA, XuW, LiuY, OhJY, SonD, KangJ, FoudehAM, ZhuC, LeeY, NiuS, LiuJ, PfattnerR, BaoZ, LeeT-W. A bioinspired flexible organic artificial afferent nerve. Science, 2018, 360: 998

[4.] QuS, SunL, ZhangS, LiuJ, LiY, LiuJ, XuW. An artificially-intelligent cornea with tactile sensation enables sensory expansion and interaction. Nat Commun, 2023, 14: 7181

[5.] JungY, KimM, JeongS, HongS, KoSH. Strain-insensitive outdoor wearable electronics by thermally robust nanofibrous radiative cooler. ACS Nano, 2024, 18: 2312

[6.] ZhangX, SunQ, LiangX, GuP, HuZ, YangX, LiuM, SunZ, HuangJ, WuG, ZuG. Stretchable and negative-Poisson-ratio porous metamaterials. Nat Commun, 2024, 15: 392

[7.] PanS, HeH, XinL, LiB, WuX, ZhangX, WangP. Super-elastic microstructured triboelectric fibers and textiles fabricated by extrusion and thermal drawing for smart-home applications. Nano Energy, 2024, 117 109259

[8.] XingT, HeA, HuangZ, LuoY, ZhangY, WangM, ShiZ, KeG, BaiJ, ZhaoS, ChenF, XuW. Silk-based flexible electronics and smart wearable textiles: progress and beyond. Chem Eng J, 2023, 474 145534

[9.] ChenJ, HeT, DuZ, LeeC. Review of textile-based wearable electronics: from the structure of the multi-level hierarchy textiles. Nano Energy, 2023, 117 108898

[10.] ZhangM, WangC, WangH, JianM, HaoX, ZhangY. Carbonized cotton fabric for high-performance wearable strain sensors. Adv Funct Mater, 2017, 27: 1604795

[11.] ZhaoX, XuZ, ZhengB, GaoC. Macroscopic assembled, ultrastrong and H₂SO₄-resistant fibres of polymer-grafted graphene oxide. Sci Rep, 2013, 3: 3164

[12.] GnidakouongJRN, GaoX, KafyA, KimJ, KimJH. Fabrication and electrical properties of regenerated cellulose-loaded exfoliated graphene nanoplatelet composites. Carbon Lett, 2019, 29: 115

[13.] JiX, XuY, ZhangW, CuiL, LiuJ. Review of functionalization, structure and properties of graphene/polymer composite fibers. Compos A Appl Sci Manuf, 2016, 87: 29

[14.] KarimN, AfrojS, TanS, HeP, FernandoA, CarrC, NovoselovKS. Scalable production of graphene-based wearable E-textiles. ACS Nano, 2017, 11: 12266

[15.] LeeHM, ChoiSY, JungA, KoSH. Highly conductive aluminum textile and paper for flexible and wearable electronics. Angew Chem Int Ed, 2013, 52: 7718

[16.] LeeHM, LeeHB, JungDS, YunJY, KoSH, ParkSB. Solution processed aluminum paper for flexible electronics. Langmuir, 2012, 28: 13127

[17.] LeTSD, PhanHP, KwonS, ParkS, JungY, MinJ, ChunBJ, YoonH, KoSH, KimSW, KimYJ. Recent advances in laser-induced graphene: mechanism, fabrication, properties, and applications in flexible electronics. Adv Funct Mater, 2022, 32: 2205158

[18.] JungY, MinJ, ChoiJ, BangJ, JeongS, PyunKR, AhnJ, ChoY, HongS, HongS, LeeJ, KoSH. Smart paper electronics by laser-induced graphene for biodegradable real-time food spoilage monitoring. Appl Mater Today, 2022, 29 101589

[19.] ManevalL, AtawaB, SergheiA, Sintes-ZydowiczN, BeyouE. In situ coupled electrical/mechanical investigations of graphene coated cationized cotton yarns with enhanced conductivity upon mechanical stretching. J Mater Chem C, 2021, 9: 14247

[20.] ZhangJ, LiuJ, ZhaoZ, HuangD, ChenC, ZhengZ, FuC, WangX, MaY, LiY, LiuZ, LiY, LiG. A facile scalable conductive graphene-coated Calotropis gigantea yarn. Cellulose, 2022, 29: 3545

[21.] NiuB, HuaT, HuH, XuB, TianX, ChanK, ChenS. A highly durable textile-based sensor as a human-worn material interface for long-term multiple mechanical deformation sensing. J Mater Chem C, 2019, 7: 14651

[22.] KimE, ArulNS, HanJI. Electrical properties of conductive cotton yarn coated with Eosin Y functionalized reduced graphene oxide. J Nanosci Nanotechnol, 2016, 16: 6061

[23.] IslamGMN, CollieS, GouldM, AliMA. Two-dimensional carbon material incorporated and PDMS-coated conductive textile yarns for strain sensing. J Coat Technol Res, 1881, 2023: 20

[24.] ZhuY, ZhaoB, LeiL, ChengZ, YuT, LiY. Facile construction of a flexible smart core-sheath flax yarns with temperature-responsive resistance for ultra-fast fire-alarm response. Chem Eng J, 2023, 471 144718

[25.] MohanVB, JayaramanK, BhattacharyyaD. Fabrication of highly conductive graphene particle-coated fiber yarns using polymeric binders through efficient coating techniques. Adv Polym Technol, 2018, 37: 3438

[26.] HuangX, QiX, BoeyF, ZhangH. Graphene-based composites. Chem Soc Rev, 2012, 41: 666

[27.] HummersWS Jr, OffemanRE. Preparation of graphitic oxide. J Am Chem Soc, 1958, 80: 1339

[28.] CaiL, QinX, XuZ, SongY, JiangH, WuY, RuanH, ChenJ. Comparison of cytotoxicity evaluation of anticancer drugs between real-time cell analysis and CCK-8 method. ACS Omega, 2019, 4: 12036

[29.] ZhangY, ChenX, ChenH, JiaM, CaiH, MaoZ, BaiY. Developing a highly-conductive and strength cotton yarn through dual shell architecture of graphene for smart wearable devices. Chem Eng J, 2023, 470 143912

[30.] ZhangY, RenH, ChenH, ChenQ, JinL, PengW, XinS, BaiY. Cotton fabrics decorated with conductive graphene nanosheet inks for flexible wearable heaters and strain sensors. ACS Appl Nano Mater, 2021, 4: 9709

[31.] LiZ, DengL, KinlochIA, YoungRJ. Raman spectroscopy of carbon materials and their composites: graphene, nanotubes and fibres. Prog Mater Sci, 2023, 135 101089

[32.] CançadoLG, JorioA, FerreiraEHM, StavaleF, AcheteCA, CapazRB, MoutinhoMVO, LombardoA, KulmalaTS, FerrariAC. Quantifying defects in graphene via Raman spectroscopy at different excitation energies. Nano Lett, 2011, 11: 3190

[33.] DresselhausMS, JorioA, HofmannM, DresselhausG, SaitoR. Perspectives on carbon nanotubes and graphene Raman spectroscopy. Nano Lett, 2010, 10: 751

[34.] WanS, LiX, ChenY, LiuN, DuY, DouS, JiangL, ChengQ. High-strength scalable MXene films through bridging-induced densification. Science, 2021, 374: 96

[35.] CuiM, RenS, ZhaoH, XueQ, WangL. Polydopamine coated graphene oxide for anticorrosive reinforcement of water-borne epoxy coating. Chem Eng J, 2018, 335: 255

[36.] PanK, FanY, LengT, LiJ, XinZ, ZhangJ, HaoL, GallopJ, NovoselovKS, HuZ. Sustainable production of highly conductive multilayer graphene ink for wireless connectivity and IoT applications. Nat Commun, 2018, 9: 5197

[37.] Martins FerreiraEH, MoutinhoMVO, StavaleF, LuccheseMM, CapazRB, AcheteCA, JorioA. Evolution of the Raman spectra from single-, few-, and many-layer graphene with increasing disorder. Phys Rev B, 2010, 82 125429

[38.] JasińskaI. Industrial washing conditions as factor that influence the cellulose structure and mechanical strength of bed linens. Sci Rep, 2023, 13: 12214

[39.] CaoC, LinZ, LiuX, JiaY, SaizE, WolfSE, WagnerHD, JiangL, ChengQ. Strong reduced graphene oxide coated bombyx mori silk. Adv Funct Mater, 2021, 31: 2102923

[40.] WanS, PengJ, LiY, HuH, JiangL, ChengQ. Use of synergistic interactions to fabricate strong, tough, and conductive artificial nacre based on graphene oxide and chitosan. ACS Nano, 2015, 9: 9830

[41.] KayabaşıG, ÖzenÖ, YılmazD. Corrigendum to a novel yarn spinning method for fabricating conductive and nanofiber-coated hybrid yarns. J Ind Text, 2020, 51: 1750S

[42.] QiX, WangW, DaiH, ZhuY, DongY, FuS-Y, NiQ, FuY. Multifunctional two-way shape memory RGO/ethylene-vinyl acetate composite yarns for electro-driven actuators and high sensitivity strain sensors. Compos A Appl Sci Manuf, 2023, 169 107521

[43.] WangL, TianM, QiX, SunX, XuT, LiuX, ZhuS, ZhangX, QuL. Customizable textile sensors based on helical core–spun yarns for seamless smart garments. Langmuir, 2021, 37: 3122

[44.] GuoT, WanZ, LiD, SongJ, RojasOJ, JinY. Intermolecular self-assembly of dopamine-conjugated carboxymethylcellulose and carbon nanotubes toward supertough filaments and multifunctional wearables. Chem Eng J, 2021, 416 128981

[45.] HeE, SunY, WangX, ChenH, SunB, GuB, ZhangW. 3D angle-interlock woven structural wearable triboelectric nanogenerator fabricated with silicone rubber coated graphene oxide/cotton composite yarn. Compos B Eng, 2020, 200 108244

[46.] MaH, WuW, CaoJ, YueB, ZhangH. Network structure and electromechanical properties of viscose-graphene conductive yarn assembles. Carbon, 2017, 114: 731

[47.] JainVK, ChatterjeeA. Graphene coated cotton nonwoven for electroconductive and UV protection applications. J Ind Text, 2021, 51: 4390S

[48.] WangJ, LiuH, YueX, ZhangD, YinR, SunH, LiuC, ShenC. Large-scale fabrication of conductive yarn with synergistic conductive coating for high-efficient strain sensing and photothermal conversion. Mater Today Nano, 2023, 24 100427

[49.] WeerasingheVT, DissanayakeDGK, PereraWPTD, TisseraND, WijesenaRN, WanasekaraND. All-organic, conductive and biodegradable yarns from core–shell nanofibers through electrospinning. RSC Adv, 2020, 10: 32875

[50.] LiX, HuH, HuaT, XuB, JiangS. Wearable strain sensing textile based on one-dimensional stretchable and weavable yarn sensors. Nano Res, 2018, 11: 5799

[51.] DingX, ZhongW, JiangH, LiM, ChenY, LuY, MaJ, YadavA, YangL, WangD. Highly accurate wearable piezoresistive sensors without tension disturbance based on weaved conductive yarn. ACS Appl Mater Interfaces, 2020, 12: 35638

[52.] LiX, HuaT, XuB. Electromechanical properties of a yarn strain sensor with graphene-sheath/polyurethane-core. Carbon, 2017, 118: 686

[53.] HongS, LeeH, LeeJ, KwonJ, HanS, SuhYD, ChoH, ShinJ, YeoJ, KoSH. Highly stretchable and transparent metal nanowire heater for wearable electronics applications. Adv Mater, 2015, 27: 4744

[54.] NamVB, ShinJ, YoonY, GiangTT, KwonJ, SuhYD, YeoJ, HongS, KoSH, LeeD. Highly stable Ni-based flexible transparent conducting panels fabricated by laser digital patterning. Adv Funct Mater, 2019, 29: 1806895

[55.] JungJ, ChoH, ChoiSH, KimD, KwonJ, ShinJ, HongS, KimH, YoonY, LeeJ, LeeD, SuhYD, KoSH. Moiré-free imperceptible and flexible random metal grid electrodes with large figure-of-merit by photonic sintering control of copper nanoparticles. ACS Appl Mater Interfaces, 2019, 11: 15773

[56.] LanX, WangY, PengJ, SiY, RenJ, DingB, LiB. Designing heat transfer pathways for advanced thermoregulatory textiles. Mater Today Phys, 2021, 17 100342

[57.] KimHG, KihmKD, LeeW, LimG, CheonS, LeeW, PyunKR, KoSH, ShinS. Effect of graphene-substrate conformity on the in-plane thermal conductivity of supported graphene. Carbon, 2017, 125: 39

[58.] PyunKR, KoSH. Graphene as a material for energy generation and control: recent progress in the control of graphene thermal conductivity by graphene defect engineering. Mater Today Energy, 2019, 12: 431

[59.] LeeW, KihmKD, KimHG, LeeW, CheonS, YeomS, LimG, PyunKR, KoSH, ShinS. Two orders of magnitude suppression of graphene's thermal conductivity by heavy dopants (Si). Carbon, 2018, 138: 98

[60.] LuoY, ZhangY, XingT, HeA, ZhaoS, HuangZ, LiangZ, LiuX, LiuY, YuY, QinY, ChenF, XuW. Full-color tunable and highly fire-retardant colored carbon fibers. Adv Fiber Mater, 2023, 5: 1618

[61.] ChenF, YangH, LiK, DengB, LiQ, LiuX, DongB, XiaoX, WangD, QinY, WangS-M, ZhangK-Q, XuW. Facile and effective coloration of dye-inert carbon fiber fabrics with tunable colors and excellent laundering durability. ACS Nano, 2017, 11: 10330

[62.] ChenF, HuangY, LiR, ZhangS, JiangQ, LuoY, WangB, ZhangW, WuX, WangF, LyuP, ZhaoS, XuW, WeiF, ZhangR. Superdurable and fire-retardant structural coloration of carbon nanotubes. Sci Adv, 2022, 8: eabn5882

[63.] BaiN, WangL, WangQ, DengJ, WangY, LuP, HuangJ, LiG, ZhangY, YangJ, XieK, ZhaoX, GuoCF. Graded intrafillable architecture-based iontronic pressure sensor with ultra-broad-range high sensitivity. Nat Commun, 2020, 11: 209

[64.] TaoLQ, ZhangKN, TianH, LiuY, WangDY, ChenYQ, YangY, RenTL. Graphene-paper pressure sensor for detecting human motions. ACS Nano, 2017, 11: 8790

Funding

National Natural Science Foundation of China(No. 52273074); the Central government guided local science and technology development fund project; Gansu Provincial Science and Technology Plan Project(22ZY2QA001); Lanzhou Science and Technology Plan Project Funding(2021-1-44)