High-Energy–Density Fiber Supercapacitors Based on Transition Metal Oxide Nanoribbon Yarns for Comprehensive Wearable Electronics

Abstract

Fiber supercapacitors (FSs) based on transition metal oxides (TMOs) have garnered considerable attention as energy storage solutions for wearable electronics owing to their exceptional characteristics, including superior comfortability and low weights. These materials are known to exhibit high energy densities, high specific capacitances, and fast redox reactions. However, current fabrication methods for these structures primarily rely on chemical deposition, often resulting in undesirable material structures and necessitating the use of additives, which can degrade the electrochemical performance of such structures. Herein, physically deposited TMO nanoribbon yarns generated via delamination engineering of nanopatterned TMO/metal/TMO trilayer arrays are proposed as potential high-performance FSs. To prepare these arrays, the target materials were initially deposited using a nanoline mold, and subsequently, the nanoribbon was suspended through selective plasma etching to obtain the desired twisted yarn structures. Because of the direct formation of TMOs on Ni electrodes, a high energy/power density and excellent electrochemical stability were achieved in asymmetric FS devices incorporating CoNixOy nanoribbon yarns and graphene fibers. Furthermore, a triboelectric nanogenerator, pressure sensor, and flexible light-emitting diode were synergistically combined with the FS. The integration of wearable electronic components, encompassing energy harvesting, energy storage, and powering sensing/display devices, is promising for the development of future smart textiles.

Graphical Abstract

References

[1.] KouL, et al. . Coaxial wet-spun yarn supercapacitors for high energy density and safe wearable electronics. Nat Commun, 2014, 5: 1-10

[2.] ZhangZ. Light-emitting materials for wearable electronics. Nat Rev Mater, 2022, 2022(7): 839-840

[3.] The many faces of wearables. Nat Electron. 2022;5:709.

[4.] LiuL, YuY, YanC, LiK, ZhengZ. Wearable energy-dense and power-dense supercapacitor yarns enabled by scalable graphene-metallic textile composite electrodes. Nat Commun, 2015, 6: 7260

[5.] ZhengF, et al. . A highly sensitive CRISPR-empowered surface plasmon resonance sensor for diagnosis of inherited diseases with femtomolar-level real-time quantification. Adv Sci, 2022, 9: 2105231

[6.] ChenZ, et al. . A CRISPR/Cas12a-empowered surface plasmon resonance platform for rapid and specific diagnosis of the Omicron variant of SARS-CoV-2. Natl Sci Rev, 2022, 9: nwac 104

[7.] XueT, et al. . Ultrasensitive detection of miRNA with an antimonene-based surface plasmon resonance sensor. Nat Commun, 2019, 10: 28

[8.] LiC, JiaR, YangY, LiaoG. A hierarchical helical carbon nanotube fiber artificial ligament. Adv Fiber Mater, 2023, 2023(5): 1549-1551

[9.] ZhengY, et al. . Electrochemical exfoliation and growth of nickel–cobalt layered double hydroxides@black phosphorus hetero-nanostructure textiles for robust foldable supercapacitors. Adv Funct Mater, 2024

[10.] ZhuX, et al. . Microfluidic-assembled covalent organic frameworks@Ti₃C₂Tx MXene vertical fibers for high-performance electrochemical supercapacitors. Adv Mater, 2023, 35: 2307186

[11.] QuG, et al. . A fiber supercapacitor with high energy density based on hollow graphene/conducting polymer fiber electrode. Adv Mater, 2016, 28: 3646-3652

[12.] RenJ, et al. . Twisting carbon nanotube fibers for both wire-shaped micro-supercapacitor and micro-battery. Adv Mater, 2013, 25: 1155-1159

[13.] LimaN, et al. . Carbon threads sweat-based supercapacitors for electronic textiles. Sci Rep, 2020, 10: 1-9

[14.] ChoiC, et al. . Stretchable, weavable coiled carbon nanotube/MnO₂/polymer fiber solid-state supercapacitors. Sci Rep, 2015, 5: 1-6

[15.] ZhaiS, ChenY. Graphene-based fiber supercapacitors. Acc Mater Res, 2022, 3: 922-934

[16.] YuD, et al. . Scalable synthesis of hierarchically structured carbon nanotube-graphene fibres for capacitive energy storage. Nat Nanotechnol, 2014, 9: 555-562

[17.] LuZ, et al. . Carbon nanotube based fiber supercapacitor as wearable energy storage. Front Mater, 2019, 2019(6): 1-14

[18.] GuanT, et al. . Recent progress of graphene fiber/fabric supercapacitors: From building block architecture, fiber assembly, and fabric construction to wearable applications. Adv Fiber Mater, 2023, 5: 896-927

[19.] LeeS, AnGH. Interface engineering of carbon fiber-based electrode for wearable energy storage devices. Adv Fiber Mater, 2023, 5: 1749-1758

[20.] ZhouY, GuanF, ZhaoF, ShenY, BaoL. High-energy-density graphene hybrid flexible fiber supercapacitors. Batter Supercaps, 2023, 6: e202200536

[21.] ZhuX, et al. . Vertical-aligned and ordered-active architecture of heterostructured fibers for high electrochemical capacitance. Adv Fiber Mater, 2024, 6: 312-328

[22.] PadmajanSS, et al. . Interface-confined high crystalline growth of semiconducting polymers at graphene fibers for high-performance wearable supercapacitors. ACS Nano, 2017, 11: 9424-9434

[23.] TianJ, CuiN, ChenP, GuoK, ChenX. High-performance wearable supercapacitors based on PANI/N-CNT@CNT fiber with a designed hierarchical core-sheath structure. J Mater Chem A Mater, 2021, 9: 20635-20644

[24.] SalmanA, et al. . Tungsten nitride-coated graphene fibers for high-performance wearable supercapacitors. Nanoscale, 2020, 12: 20239-20249

[25.] LimL, et al. . All-in-one graphene based composite fiber: Toward wearable supercapacitor. ACS Appl Mater Interfaces, 2017, 9: 39576-39583

[26.] CaiW, et al. . Transition metal sulfides grown on graphene fibers for wearable asymmetric supercapacitors with high volumetric capacitance and high energy density. Sci Rep, 2016, 6: 1-9

[27.] YuanS, et al. . Recent progress on transition metal oxides as advanced materials for energy conversion and storage. Energy Storage Mater, 2021, 2021(42): 317-369

[28.] TengXL, SunXT, GuanL, HuH, WuMB. Self-supported transition metal oxide electrodes for electrochemical energy storage. Tungsten, 2020, 2020(2): 337-361

[29.] LeiZ, et al. . Recent advances of layered-transition metal oxides for energy-related applications. Energy Storage Mater, 2021, 36: 514-550

[30.] WeiZY, et al. . Progress in ceramic materials and structure design toward advanced thermal barrier coatings. J Adv Ceram, 2022, 11: 985-1068

[31.] DelbariSA, et al. . Transition metal oxide-based electrode materials for flexible supercapacitors: A review. J Alloys Compd, 2021, 857: 158281

[32.] GeorgakilasV, et al. . Noncovalent functionalization of graphene and graphene oxide for energy materials, biosensing, catalytic, and biomedical applications. Chem Rev, 2016, 116: 5464-5519

[33.] AhnJ, et al. . Nanotransfer-on-things: From rigid to stretchable nanophotonic devices. ACS Nano, 2023

[34.] AhnJ, et al. . Nanoscale three-dimensional fabrication based on mechanically guided assembly. Nat Commun, 2023, 14: 833

[35.] LiuLY, et al. . Synthesis of Co–Ni oxide microflowers as a superior anode for hybrid supercapacitors with ultralong cycle life. Chin Chem Lett, 2017, 28: 206-212

[36.] KaracaE, GökcenD, PekmezNÖ, PekmezK. Electrochemical synthesis of PPy composites with nanostructured MnOx, CoOx, NiOx, and FeOx in acetonitrile for supercapacitor applications. Electrochim Acta, 2019, 305: 502-513

[37.] PengJ, JeffreySG. A figure of merit for flexibility. Science, 2019, 366: 690-691

[38.] ChenYS, et al. . Microscopic mechanism for unipolar resistive switching behaviour of nickel oxides. J Phys D Appl Phys, 2012, 45: 065303

[39.] WangM, et al. . Efficiently enhancing electrocatalytic activity of α-MnO2 nanorods/N-doped ketjenblack carbon for oxygen reduction reaction and oxygen evolution reaction using facile regulated hydrothermal treatment. Catalysts, 2018, 8: 138

[40.] LiXC, et al. . Coherent nanoscale cobalt/cobalt oxide heterostructures embedded in porous carbon for the oxygen reduction reaction. RSC Adv, 2018, 8: 28625-28631

[41.] Wang R, Wu J. Structure and basic properties of ternary metal oxides and their prospects for application in supercapacitors. In: Metal oxides in supercapacitors. Elsevier Inc.; 2017. p. 99–132.

[42.] XieJ, et al. . Puzzles and confusions in supercapacitor and battery: theory and solutions. J Power Sour, 2018, 401: 213-223

[43.] SahooS, KumarR, JoanniE, SinghRK, ShimJJ. Advances in pseudocapacitive and battery-like electrode materials for high performance supercapacitors. J Mater Chem A Mater, 2022, 10: 13190-13240

[44.] Reddy IntaH, KoppisettiHVSRM, GhoshS, RoyA, MahalingamV. Ni3Se4 nanostructure as a battery-type positive electrode for hybrid capacitors. ChemElectroChem, 2023, 10: 1-11

[45.] KushwahaV, MandalKD, GuptaA, SinghP. Ni0.5Co0.5S nano-chains: a high-performing intercalating pseudocapacitive electrode in asymmetric supercapacitor (ASC) mode for the development of large-scale energy storage devices. Dalton Trans, 2024, 53: 5435-5452

[46.] ChoiC, et al. . Improvement of system capacitance via weavable superelastic biscrolled yarn supercapacitors. Nat Commun, 2016, 7: 1-8

[47.] MeddingsN, et al. . Application of electrochemical impedance spectroscopy to commercial Li-ion cells: A review. J Power Sour, 2020, 480: 228742

[48.] PechD, et al. . Ultrahigh-power micrometre-sized supercapacitors based on onion-like carbon. Nat Nanotechnol, 2010, 5: 651-654

[49.] El-KadyMF, KanerRB. Scalable fabrication of high-power graphene micro-supercapacitors for flexible and on-chip energy storage. Nat Commun, 2013, 4: 1475

[50.] KimMS, et al. . Skin-like omnidirectional stretchable platform with negative Poisson’s ratio for wearable strain–pressure simultaneous sensor. Adv Funct Mater, 2023, 33: 1-10

[51.] JungY, et al. . Spherical micro/nano hierarchical structures for energy and water harvesting devices. Small Methods, 2022, 2200248: 1-11

[52.] ZhaoZJ, et al. . Wafer-scale, highly uniform, and well-arrayed suspended nanostructures for enhancing the performance of electronic devices. Nanoscale, 2022, 14: 1136-1143

[53.] JeongY, et al. . Biomimetic, programmable, and part-by-part maneuverable single-body shape-morphing film. Adv Intell Syst, 2023, 5: 1-12

[54.] ZhaoZJ, et al. . Large-area nanogap-controlled 3D nanoarchitectures fabricated via layer-by-layer nanoimprint. ACS Nano, 2021, 15: 503-514

[55.] ZhaoZJ, et al. . Shape-controlled and well-arrayed heterogeneous nanostructures via melting point modulation at the nanoscale. ACS Appl Mater Interfaces, 2021, 13: 3358-3368

[56.] AhnJ, et al. . All-recyclable triboelectric nanogenerator for sustainable ocean monitoring systems. Adv Energy Mater, 2022, 2201341: 1-11

[57.] AhnJ, et al. . Morphology-controllable wrinkled hierarchical structure and its application to superhydrophobic triboelectric nanogenerator. Nano Energy, 2021, 85: 105978

[58.] Ahn J, et al. Nanoribbon yarn with versatile inorganic materials. Small. 2024. https://doi-org-ssl.oca.korea.ac.kr/10.1002/smll.202311736.

Funding

the National Creative Research Initiative (CRI) Center for Multi-Dimensional Directed Nanoscale Assembly(2015R1A3A2033061); Creative Challenge research grant(RS-2023-00248902); the Ministry of Trade, Industry, & Energy (MI, Korea)(20018235, Development of an inline nano-imprinter for nano photonic device); the Ministry of Culture, Sports, and Tourism, and the Korea Creative Content Agency(R2022020033); National Research Foundation of Korea (NRF) grant funded by the Korean government(2021R1A2C3008742); by the Ministry of SMEs and Startups(MSS, Korea)(by the Collabo R&D between Industry, Academy, and Research Institute (RS-2024-00428937)); Korea Advanced Institute of Science and Technology