Vertical-Aligned and Ordered-Active Architecture of Heterostructured Fibers for High Electrochemical Capacitance

Abstract

Architecture of fibrous building blocks with ordered structure and high electroactivity that enables quick charge kinetic transport/intercalation is necessary for high-energy-density electrochemical supercapacitors. Herein, we report a heterostructured molybdenum disulfide@vertically aligned graphene fiber (MoS₂@VA-GF), wherein well-defined MoS₂ nanosheets are decorated on vertical graphene fibers by C–O–Mo covalent bonds. Benefiting from uniform microfluidic self-assembly and confined reactions, it is realized that the unique characteristics of a vertical-aligned skeleton, large faradic activity, in situ interfacial connectivity and high-exposed surface/porosity remarkably create efficiently directional ionic pathways, interfacial electron mobility and pseudocapacitive accessibility for accelerating charge transport and intercalation/de-intercalation. Resultant MoS₂@VA-GF exhibits large gravimetric capacitance (564 F g⁻¹) and reversible redox transitions in 1 M H₂SO₄ electrolyte. Furthermore, the MoS₂@VA-GF-based solid-state supercapacitors deliver high energy density (45.57 Wh kg⁻¹), good cycling stability (20,000 cycles) and deformable/temperature-tolerant capability. Beyond that, supercapacitors can realize actual applications of powering multicolored optical fiber lamps, wearable watch, electric fans and sunflower toys.

Keywords

Vertical-aligned structure / Ion directional diffusion / Microfluidic assembly / Electrochemical supercapacitors / High capacitance / Self-powered applications

References

[1] Saha T, Del Cano RD, Mahato K, De la Paz E, Chen CR, Ding SC, Yin L, Wang J. Wearable electrochemical glucose sensors in diabetes management: a comprehensive review. Chem Rev, 2023, 123: 7854,

[2] Zeng K, Shi X, Tang C, Liu T, Peng H. Design, fabrication and assembly considerations for electronic systems made of fibre devices. Nat Rev Mater, 2023, 8: 552,

[3] Ramada DL, Vries J, Vollenbroek J, Noor N, Beek O, Mihaila SM, Wieringa F, Masereeuw R, Gerritsen K, Stamatialis D. Portable, wearable and implantable artificial kidney systems: needs, opportunities and challenges. Nat Rev Nephrol, 2023, 19: 481,

[4] Sahasrabudhe A, Anikeeva P. Wireless microelectronic fibers to discover gut and brain pathways. Nat Biotechnol, 2023,

[5] Yoo G, Lee YG, Im B, Kim DG, Jo YR, An GH. Integrated solution for a stable and high-performance zinc-ion battery using an electrolyte additive. Energy Storage Mater, 2023, 61,

[6] Fan XY, Zhong C, Liu J, Ding J, Deng YD, Han XP, Zhang L, Hu WB, Wilkinson DP, Zhang JJ. Opportunities of flexible and portable electrochemical devices for energy storage: expanding the spotlight onto semi-solid/solid electrolytes. Chem Rev, 2022, 122: 17155,

[7] Jia BB, Zhang BH, Cai Z, Yang XY, Li LD, Guo L. Construction of amorphous/crystalline heterointerfaces for enhanced electrochemical processes. eScience, 2023, 3: 100112,

[8] Wang H, Li JM, Li K, Lin YP, Chen JM, Gao LJ, Nicolosi V, Xiao X, Lee JM. Transition metal nitrides for electrochemical energy applications. Chem Soc Rev, 2021, 50: 1354,

[9] Zheng Y, Man ZM, Zhang Y, Wu G, Lu WY, Chen WX. High-Performance stretchable supercapacitors based on centrifugal electrospinning-directed hetero-structured graphene–polyaniline hierarchical fabric. Adv Fiber Mater, 2023,

[10] Cho Y, Pak S, Lee YG, Hwang JS, Giraud P, An GH, Cha SN. Hybrid smart fiber with spontaneous self-charging mechanism for sustainable wearable electronics. Adv Funct Mater, 2020, 30: 1908479,

[11] Ma WJ, Zhang Y, Pan SW, Cheng YH, Shao ZY, Xiang HX, Chen GY, Zhu LP, Weng W, Bai H, Zhu MF. Smart fibers for energy conversion and storage. Chem Soc Rev, 2021, 50: 7009,

[12] Lee S, An GH. Interface engineering of carbon fiber-based electrode for wearable energy storage devices. Adv Fiber Mater, 2023,

[13] Khudiyev T, Lee JT, Cox JR, Argentieri E, Loke G, Yuan R, Noel GH, Tatara R, Yu Y, Logan F, Joannopoulos J, Shao-Horn Y, Fink Y. 100 m long thermally drawn supercapacitor fibers with applications to 3D printing and textiles. Adv Mater, 2020, 32: 2004971,

[14] Guan TX, Li ZM, Qiu DC, Wu G, Wu J, Zhu LP, Zhu MF, Bao NZ. 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,

[15] Chen SH, Ma WJ, Cheng YH, Weng Z, Sun B, Wang L, Chen WP, Li F, Zhu MF, Cheng HM. Scalable non-liquid-crystal spinning of locally aligned graphene fibers for high-performance wearable supercapacitors. Nano Energy, 2015, 15: 642,

[16] Xin GQ, Zhu WG, Deng YX, Cheng J, Zhang LT, Chung AJ, De S, Lian J. Microfluidics-enabled orientation and microstructure control of macroscopic graphene fibres. Nat Nanotechnol, 2019, 14: 168,

[17] Zhu XL, Zhang Y, Man ZM, Lu WY, Chen W, Xu JH, Bao NZ, Chen WX, Wu G. Microfluidic-assembled covalent organic frameworks@Ti3C2TX MXene vertical fibers for high-performance electrochemical supercapacitors. Adv Mater, 2023,

[18] Zhou ZJ, Li P, Man ZM, Zhu XL, Ye SY, Lu WY, Wu G, Chen WX. Multiscale dot-wire-sheet heterostructured nitrogen-doped carbon dots-Ti₃C₂Tx/Silk nanofibers for high-performance fiber-shaped supercapacitors. Angew Chem Int Ed, 2023, 62,

[19] Lee K, Shang Y, Bobrin VA, Kuchel R, Kundu D, Corrigan N, Boyer C. 3D printing nanostructured solid polymer electrolytes with high modulus and conductivity. Adv Mater, 2022, 34: 2204816,

[20] Zhai SL, Karahan HE, Wei L, Chen XC, Zhou Z, Wang X, Chen Y. Hydrothermal assembly of micro-nano-integrated core-sheath carbon fibers for high-performance all-carbon micro-supercapacitors. Energy Storage Mater, 2017, 9: 221,

[21] Ni XP, Li KM, Li CL, Wu QQ, Liu CL, Chen HF, Wu QL, Ju AQ. Construction of NiCo₂O₄ nanoflake arrays on cellulose-derived carbon nanofibers as a freestanding electrode for high-performance supercapacitors. Front Chem Sci Eng, 2023, 17: 691,

[22] Wu G, Sun SY, Zhu XL, Ma ZM, Zhang YM, Bao NZ. Microfluidic fabrication of hierarchical-ordered ZIF-L(Zn)@Ti₃C₂Tx core-sheath fibers for high-performance asymmetric supercapacitors. Angew Chem Int Ed, 2022, 61: 202115559,

[23] Cui MQ, Wang ZN, Jiang YY, Wang H. Engineering the grain boundary: a promising strategy to configure NiCoP₄O₁₂/NiCoP nanowire arrays for ultra-stable supercapacitor. Front Chem Sci Eng, 2022, 16: 1259,

[24] Shin H, Eom W, Lee KH, Jeong W, Kang DJ, Han TH. Highly Electroconductive and mechanically strong Ti₃C₂Tx MXene fibers using a deformable MXene gel. ACS Nano, 2021, 15: 3320,

[25] Wang L, Xu SG, Wang Z, Yang EE, Jiang WY, Zhang SH, Jian XG, Hu FY. A nano fiber–gel composite electrolyte with high Li⁺ transference number for application in quasi-solid batteries. eScience, 2023, 3: 100090,

[26] Feng MY, Zhang Y, Zhu XL, Chen WX, Lu WY, Wu G. Interface-anchored covalent organic frameworks@amino-modified Ti₃C₂Tx MXene on Nylon 6 film for high-performance deformable supercapacitors. Angew Chem Int Ed, 2023, 62,

[27] Wu G, Tan PF, Wu XJ, Peng L, Cheng HY, Wang CF, Chen W, Yu ZY, Chen S. High-performance wearable micro-supercapacitors based on microfluidic-directed nitrogen-doped graphene fiber electrodes. Adv Funct Mater, 2017, 27: 1702493,

[28] Qu GX, Cheng JL, Li XD, Yuan DM, Chen PN, Chen XL, Wang B, Peng HS. A fiber supercapacitor with high energy density based on hollow graphene/conducting polymer fiber electrode. Adv Mater, 2016, 28: 3646,

[29] Meng ZY, Qiu ZM, Shi YX, Wang SX, Zhang GX, Pi YC, Pang H. Micro/nano metal–organic frameworks meet energy chemistry: a review of materials synthesis and applications. eScience, 2023, 3: 100092,

[30] Guo YQ, Hong XF, Wang Y, Li Q, Meng JS, Dai RT, Liu X, He L, Mai LQ. Multicomponent hierarchical Cu-doped NiCo-LDH/CuO double arrays for ultralong-life hybrid fiber supercapacitor. Adv Funct Mater, 2019, 29: 1809004,

[31] Wang X, Li H, Li H, Lin S, Ding W, Zhu XG, Sheng ZG, Wang H, Zhu XB, Sun YP. 2D/2D 1T-MoS₂/Ti₃C₂ MXene heterostructure with excellent supercapacitor performance. Adv Funct Mater, 2020, 30: 0190302,

[32] Xiao BH, Cai WJ, Wu PY, Xiao K, Liu ZQ. Hierarchically structured three-dimensional carbon-based integrated electrodes with enhanced pseudocapacitance and deformability. Renewables, 2023, 1: 227,

[33] Wu TY, Ma ZY, He YY, Wu XJ, Tang B, Yu ZY, Wu G, Chen S, Bao NZ. A covalent black phosphorus/metal-organic framework hetero-nanostructure for high-performance flexible supercapacitors. Angew Chem Int Ed, 2021, 60: 10366,

[34] Lu Z, Foroughi J, Wang CY, Long HR, Wallace GG. Superelastic hybrid CNT/Graphene fibers for wearable energy storage. Adv Energy Mater, 2018, 8: 1702047,

[35] Zhang JZ, Seyedin S, Qin S, Wang ZY, Moradi S, Yang FL, Lynch PA, Yang WR, Liu JQ, Wang XG, Razal JM. Highly conductive Ti₃C₂Tx MXene hybrid fibers for flexible and elastic fiber-shaped supercapacitors. Small, 2019, 15: 1804732,

[36] Huang H, Zhao YP, Cong TZ, Li CW, Wen NX, Zuo XQ, Guo Y, Zhang H, Fan Z, Pan LJ. Flexible and alternately layered high-loading film electrode based on 3D carbon nanocoils and PEDOT:PSS for high-energy-density supercapacitor. Adv Funct Mater, 2022, 32: 2110777,

[37] Choi C, Kim KM, Kim KJ, Lepro X, Spinks GM, Baughman RH, Kim SJ. Improvement of system capacitance via weavable superelastic biscrolled yarn supercapacitors. Nat Commun, 2016, 7: 13811,

[38] An GH, Hong J, Pak S, Cho Y, Lee S, Hou B, Cha S. 2D Metal Zn nanostructure electrodes for high-performance Zn ion supercapacitors. Adv Energy Mater, 2020, 10: 1902981,

[39] Lee YG, Lee J, An GH. Surface engineering of carbon via coupled porosity tuning and heteroatom-doping for high-performance flexible fibrous supercapacitors. Adv Funct Mater, 2021, 31: 2104256,

[40] Lee YG, Yoo G, Jo YR, An HR, Koo BR, An GH. Interfacial electrochemical media-engineered tunable vanadium zinc hydrate oxygen defect for enhancing the redox reaction of Zinc-Ion hybrid supercapacitors. Adv Energy Mater, 2023, 13: 2300630,

[41] Li Q, Cheng HY, Wu XJ, Wang CF, Wu G, Chen S. Enriched carbon dots/graphene microfibers towards high-performance micro-supercapacitors. J Mater Chem A, 2018, 6: 14112,

[42] Yuan YJ, Jiang L, Li X, Zuo P, Zhang XQ, Lian YL, Ma YL, Liang MS, Zhao Y, Qu LT. Ultrafast shaped laser induced synthesis of MXene quantum dots/graphene for transparent supercapacitors. Adv Mater, 2022, 34,

[43] Zhao CH, Zhou YN, Ge ZX, Zhao CJ, Qian XZ. Facile construction of MoS₂/RCF electrode for high-performance supercapacitor. Carbon, 2018, 127: 699,

[44] Ji HM, Liu C, Wang T, Chen J, Mao ZN, Zhao J, Hou WH, Yang G. Porous hybrid composites of few-layer MoS₂ nanosheets embedded in a carbon matrix with an excellent supercapacitor electrode performance. Small, 2015, 11: 6480,

[45] Yang W, He L, Tian XC, Yan MY, Yuan H, Liao XB, Meng JS, Hao ZM, Mai LQ. Carbon-MEMS-based alternating stacked MoS₂@rGO-CNT micro-supercapacitor with high capacitance and energy density. Small, 2017, 13: 1700639,

[46] Cheng ZB, Chen YL, Yang YS, Zhang LJ, Pan H, Fan X, Xiang SC, Zhang ZJ. Metallic MoS₂ nanoflowers decorated graphene nanosheet catalytically boosts the volumetric capacity and cycle life of lithium-sulfur batteries. Adv Energy Mater, 2021, 11: 2003718,

[47] Silveira Firmiano EG, Rabelo AC, Dalmaschio CJ, Pinheiro AN, Pereira EC, Schreiner WH, Leite ER. Supercapacitor electrodes obtained by directly bonding 2D MoS₂ on reduced graphene oxide. Adv Energy Mater, 2014, 4: 1301380,

[48] Tang C, Zhong L, Zhang BS, Wang HF, Zhang Q. 3D Mesoporous van der waals heterostructures for trifunctional energy electrocatalysis. Adv Mater, 2018, 30: 1705110,

[49] Cao LJ, Yang SB, Gao W, Liu Z, Gong YJ, Ma LL, Shi G, Lei SD, Zhang YH, Zhang ST, Vajtai R, Ajayan PM. Direct laser-patterned micro-supercapacitors from paintable MoS₂ films. Small, 2013, 9: 2905,

[50] Han FM, Qian O, Meng GW, Lin D, Chen G, Zhang SP, Pan QJ, Zhang X, Zhu XG, Wei BQ. Structurally integrated 3D carbon tube grid-based high-performance filter capacitor. Sci, 2022, 377: 1004,

[51] Xiao BH, Li JX, Xu HY, Huang JL, Luo YL, Xiao K, Liu ZQ. Polymer chainmail: steric hindrance and charge compensation of anion-doped PEDOT to boost stress deformation of compressible supercapacitor. Angew Chem Int Ed, 2023, 62,

[52] Wang BJ, Wu QQ, Sun H, Zhang J, Ren J, Luo YF, Wang M, Peng HS. An intercalated graphene/(molybdenum disulfide) hybrid fiber for capacitive energy storage. J Mater Chem A, 2017, 5: 925,

[53] Jian XL, Li HB, Li H, Li YX, Shang YY. Flexible and freestanding MoS₂/rGO/CNT hybrid fibers for high-capacity all-solid supercapacitors. Carbon, 2021, 172: 132,

[54] Wang DH, Han CP, Mo FN, Yang Q, Zhao YW, Li Q, Liang GJ, Dong BB, Zhi CY. Energy density issues of flexible energy storage devices. Energy Storage Mater, 2020, 28: 264,

[55] Xia Y, Mathis TS, Zhao MQ, Anasori B, Dang A, Zhou Z, Cho H, Gogotsi Y, Yang S. Thickness-independent capacitance of vertically aligned liquid-crystalline MXenes. Nature, 2018, 557: 409,

[56] He NF, Shan WT, Wang JL, Pan Q, Qu JG, Wang GF, Gao W. Mordant inspired wet-spinning of graphene fibers for high performance flexible supercapacitors. J Mater Chem A, 2019, 7: 6869,

[57] Cong HP, Ren XC, Wang P, Yu SH. Wet-spinning assembly of continuous, neat, and macroscopic graphene fibers. Sci Rep, 2012, 2: 613,

[58] Liu S, Nie CB, Zhou DH, Shen J, Feng SL. Direct growth of vertical structure MoS₂ nanosheets array film via CVD method for photodetection. Phys E, 2020, 117,

[59] Teng YQ, Zhao HL, Zhang ZJ, Li ZL, Xia Q, Zhang Y, Zhao LN, Du XF, Du ZH, Lv PP, Swierczek K. MoS₂ nanosheets vertically grown on graphene sheets for lithium-ion battery anodes. ACS Nano, 2016, 10: 8526,

[60] Mahmood Q, Park SK, Kwon KD, Chang SJ, Hong JY, Shen G, Jung YM, Park TJ, Khang SW, Kim WS, KongJ PHS. Transition from diffusion-controlled intercalation into extrinsically pseudocapacitive charge storage of MoS₂ by nanoscale heterostructuring. Adv Energy Mater, 2016, 6: 1501115,

[61] Xin GQ, Yao TK, Sun HT, Scott SM, Shao DL, Wang GK, Lian J. Highly thermally conductive and mechanically strong graphene fibers. Sci, 2015, 349: 1083,

[62] He JR, Hartmann G, Lee M, Hwang GS, Chen YF, Manthiram A. Freestanding 1T MoS₂/graphene heterostructures as a highly efficient electrocatalyst for lithium polysulfides in Li-S batteries. Energy Environ Sci, 2019, 12: 344,

[63] Xie XQ, Ao ZM, Su DW, Zhang JQ, Wang GX. MoS₂/Graphene composite anodes with enhanced performance for sodium-ion batteries: the role of the two-dimensional heterointerface. Adv Funct Mater, 2015, 25: 1393,

[64] Wang LJ, Liu FH, Zhao BY, Ning YS, Zhang LF, Bradley R, Wu WP. Carbon nanobowls filled with MoS₂ nanosheets as electrode materials for supercapacitors. ACS Appl Nano Mater, 2020, 3: 6448,

[65] Soon JM, Loh KP. Electrochemical double-layer capacitance of MoS₂ nanowall films. Electrochem Solid-State Lett, 2007, 10: A250,

[66] Feng N, Meng RJ, Zu LH, Feng YT, Peng CX, Huang JM, Liu GL, Chen BJ, Yang JH. A polymer-direct-intercalation strategy for MoS₂/carbon-derived heteroaerogels with ultrahigh pseudocapacitance. Nat Commun, 2019, 10: 1372,

[67] Pan QC, Zhang QB, Zheng FH, Liu YZ, Li YP, Ou X, Xiong XH, Yang CH, Liu ML. Construction of MoS₂/C hierarchical tubular heterostructures for high-performance sodium ion batteries. ACS Nano, 2018, 12: 12578,

[68] Chen XL, Qiu LB, Ren J, Guan GZ, Lin HJ, Zhang ZT, Chen PN, Wang YG, Peng HS. Novel electric double-layer capacitor with a coaxial fiber structure. Adv Mater, 2013, 25: 6436,

[69] Zhang ZT, Deng J, Li XY, Yang ZB, He SS, Chen XL, Guan GZ, Ren J, Peng HS. Superelastic supercapacitors with high performances during stretching. Adv Mater, 2015, 27: 356,

[70] Zhang JZ, Uzun S, Seyedin SY, Lynch PA, Akuzum B, Wang ZY, Qin S, Alhabeb M, Shuck CE, Lei WE, Kumbur EC, Yang WR, Wang XG, Dion G, Razal JM, Gogotsi Y. Additive-free MXene liquid crystals and fibers. ACS Cent Sci, 2020, 6: 254,

[71] Zhang WY, Wei S, Wu YN, Wang YL, Zhang M, Roy D, Wang H, Yuan JY, Zhao Q. Poly(Ionic Liquid)-derived graphitic nanoporous carbon membrane enables superior supercapacitive energy storage. ACS Nano, 2019, 13: 10261,

[72] Yu N, Yin H, Zhang W, Liu Y, Tang ZY, Zhu MQ. High-performance fiber-shaped all-solid-state asymmetric supercapacitors based on ultrathin MnO₂ nanosheet/carbon fiber cathodes for wearable electronics. Adv Energy Mater, 2016, 6: 1501458,

[73] Wen JF, Xu BG, Zhou JY, Xu JT, Chen YJ. 3D patternable supercapacitors from hierarchically architected porous fiber composites for wearable and waterproof energy storage. Small, 2019, 15: 1901313,

[74] Zhai T, Lu XH, Ling YC, Yu MH, Wang GM, Liu TY, Liang CL, Tong YX, Li Y. A new benchmark capacitance for supercapacitor anodes by mixed-valence sulfur-doped V₆O₁₃-x. Adv Mater, 2014, 26: 5869,

[75] Li XL, Li XD, Cheng JL, Yuan DM, Ni W, Guan Q, Gao LZ, Wang B. Fiber-shaped solid-state supercapacitors based on molybdenum disulfide nanosheets for a self-powered photodetecting system. Nano Energy, 2016, 21: 228,

[76] Tian JY, Cui NJ, Chen PN, Guo KK, Chen XL. High-performance wearable supercapacitors based on PANI/N-CNT@CNT fiber with a designed hierarchical core-sheath structure. J Mater Chem A, 2021, 9: 20635,

[77] Zhou WJ, Zhou K, Liu XJ, Hu RZ, Liu H, Chen SW. Flexible wire-like all-carbon supercapacitors based on porous core-shell carbon fibers. J Mater Chem A, 2014, 2: 7250,

Funding

Innovative Research Group Project of the National Natural Science Foundation of China(22278378); Natural Science Foundation of Jiangsu Province(BK20211592); Science and Technology Program of Zhejiang Province(22212011-Y)