Flexible all-solid-state micro-supercapacitor based on Ni fiber electrode coated with MnO<sub>2</sub> and reduced graphene oxide <italic>via</italic> electrochemical deposition

Jinhua Zhou; Ningna Chen; You Ge; Hongli Zhu; Xiaomiao Feng; Ruiqing Liu; Yanwen Ma; Lianhui Wang; Wenhua Hou

doi:10.1007/s40843-017-9168-9

SCIENCE CHINA Materials

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SCIENCE CHINA Materials, Volume 61, Issue 2: 243-253(2018) https://doi.org/10.1007/s40843-017-9168-9

Flexible all-solid-state micro-supercapacitor based on Ni fiber electrode coated with MnO₂ and reduced graphene oxide via electrochemical deposition

Jinhua Zhou^1,2,?, Ningna Chen^2,?, You Ge¹, Hongli Zhu¹, Xiaomiao Feng^1,*, Ruiqing Liu¹, Yanwen Ma¹, Lianhui Wang¹, Wenhua Hou^2,*

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ReceivedSep 5, 2017
AcceptedNov 23, 2017
PublishedJan 19, 2018

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Abstract

Flexible and micro-sized energy conversion/storage components are extremely demanding in portable and multifunctional electronic devices, especially those small, flexible, roll-up and even wearable ones. Here in this paper, a two-step electrochemical deposition method has been developed to coat Ni fibers with reduced graphene oxide and MnO₂ subsequently, giving rise to Ni@reduced-graphene-oxide@MnO₂ sheath-core flexible electrode with a high areal specific capacitance of 119.4 mF cm^?2 at a current density of 0.5?mA cm^?2 in 1?mol?L^?1 Na₂SO₄ electrolyte. Using polyvinyl alcohol (PVA)-LiCl as a solid state electrolyte, two Ni@reduced-graphene-oxide@MnO₂ flexible electrodes were assembled into a freestanding, lightweight, symmetrical fiber-shaped micro-supercapacitor device with a maximum areal capacitance of26.9 mF cm^?2. A high power density of 0.1?W cm^?3 could be obtained when the energy density was as high as 0.27?mW?h?cm^?3. Moreover, the resulting micro-supercapacitor device also demonstrated good flexibility and high cyclic stability. The present work provides a simple, facile and low-cost method for the fabrication of flexible, lightweight and wearable energy conversion/storage micro-devices with a high-performance.

Funded by

the Ministry of Education of China(IRT1148)

the Program of NUPT(NY214088)

and the Open Research Fund of State Key Laboratory of Bioelectronics of Southeast University(I2015010)

the National Natural Science Foundation of China(20905038)

Synergistic Innovation Center for Organic Electronics and Information Displays

Jiangsu Province “Six Talent Peak”(2015-JY-015)

Jiangsu Provincial Natural Science Foundation(BK20141424)

Acknowledgment

This work was supported by the Ministry of Education of China (IRT1148), the National Natural Science Foundation of China (51772157 and 21173116), Synergistic Innovation Center for Organic Electronics and Information Displays, Jiangsu Province “Six Talent Peak” (2015-JY-015), Jiangsu Provincial Natural Science Foundation (BK20141424), the Program of Nanjing University of Posts and Telecommunications (NY214088), and the Open Research Fund of State Key Laboratory of Bioelectronics of Southeast University (I2015010).

Interest statement

The authors declare no conflict of interest.

Contributions statement

Feng X and Ma Y designed and engineered this work; Zhou J, Chen N, Ge Y, Zhu H carried out the experiments. Zhou J and Hou W wrote this paper. All authors contributed to the general discussion.

Author information

Jinhua Zhou received her MSc degree under the supervision of Prof. Xiaomiao Feng in the Department of Materials Chemistry at the Nanjing University of Posts and Telecommunications in 2016. She is currently a PhD under the supervision of Prof. Wenhua Hou at Nanjing University. Her research is mainly focused on the synthesis of 2D materials, and their application for energy conversion and storage devices.

Ningna Chen obtained her MSc degree from Nanjing University of Posts & Telecommunications in 2015. Currently, she is pursuing her PhD degree under the supervision of Prof. Wenhua Hou at Nanjing University. Her research is mainly focused on the synthesis of two-dimensional layered transition metal oxide nanomaterials, and their application for energy conversion and storage devices.

Xiaomiao Feng is a Professor in the Department of Materials Chemistry at the Nanjing University of Posts and Telecommunications. She received her PhD from Nanjing University, Nanjing (China) in 2007. Between July 2012 and July 2013 she joined the research group of Prof. J. Wang at the Department of Nanoengineering, University of California, San Diego as a visiting scholar. Her research interests include nanomaterials, naonomachines, biosensors and super capacitors.

Wenhua Hou is a professor in the School of Chemistry and Chemical Engineering at Nanjing University. He received his BS (1985) and PhD (1993) in chemistry from Nanjing University. He worked as visiting scholar at the State University of New York at Albany and University of California, San Diego. His research interests include the synthesis of 2D layer nanomaterials for potocatalysis and energy storage.

Supplement

Supporting data are available in the online version of this paper.

References

[1] Cheng JP, Zhang J, Liu F. Recent development of metal hydroxides as electrode material of electrochemical capacitors. RSC Adv, 2014, 4: 38893-38917 CrossRef Google Scholar

[2] Liu S, Sun S, You XZ. Inorganic nanostructured materials for high performance electrochemical supercapacitors. Nanoscale, 2014, 6: 2037-2045 CrossRef PubMed ADS Google Scholar

[3] Wang G, Zhang L, Zhang J. A review of electrode materials for electrochemical supercapacitors. Chem Soc Rev, 2012, 41: 797-828 CrossRef PubMed Google Scholar

[4] Yu L, Zhang G, Yuan C, et al. Hierarchical NiCo₂O₄@MnO₂ core-shell heterostructured nanowire arrays on Ni foam as high-performance supercapacitor electrodes. Chem Commun, 2013, 49: 137-139 CrossRef PubMed Google Scholar

[5] Wang K, Zhang X, Sun X, et al. Conducting polymer hydrogel materials for high-performance flexible solid-state supercapacitors. Sci China Mater, 2016, 59: 412-420 CrossRef Google Scholar

[6] Frackowiak E, Béguin F. Carbon materials for the electrochemical storage of energy in capacitors. Carbon, 2001, 39: 937-950 CrossRef Google Scholar

[7] Futaba DN, Hata K, Yamada T, et al. Shape-engineerable and highly densely packed single-walled carbon nanotubes and their application as super-capacitor electrodes. Nat Mater, 2006, 5: 987-994 CrossRef PubMed ADS Google Scholar

[8] Stoller MD, Park S, Zhu Y, et al. Graphene-based ultracapacitors. Nano Lett, 2008, 8: 3498-3502 CrossRef PubMed ADS Google Scholar

[9] Wang DW, Li F, Zhao J, et al. Fabrication of graphene/polyaniline composite paper via in situ anodic electropolymerization for high-performance flexible electrode. ACS Nano, 2009, 3: 1745-1752 CrossRef PubMed Google Scholar

[10] Hu CC, Chang KH, Lin MC, et al. Design and tailoring of the nanotubular arrayed architecture of hydrous RuO₂ for next generation supercapacitors. Nano Lett, 2006, 6: 2690-2695 CrossRef PubMed ADS Google Scholar

[11] Wang H, Casalongue HS, Liang Y, et al. Ni(OH)₂ nanoplates grown on graphene as advanced electrochemical pseudocapacitor materials. J Am Chem Soc, 2010, 132: 7472-7477 CrossRef PubMed Google Scholar

[12] Feng X, Yan Z, Chen N, et al. The synthesis of shape-controlled MnO₂/graphene composites via a facile one-step hydrothermal method and their application in supercapacitors. J Mater Chem A, 2013, 1: 12818-12825 CrossRef Google Scholar

[13] Wang H, Deng J, Chen Y, et al. Hydrothermal synthesis of manganese oxide encapsulated multiporous carbon nanofibers for supercapacitors. Nano Res, 2016, 9: 2672-2680 CrossRef Google Scholar

[14] Rakhi RB, Chen W, Hedhili MN, et al. Enhanced rate performance of mesoporous Co₃O₄ nanosheet supercapacitor electrodes by hydrous RuO₂ nanoparticle decoration. ACS Appl Mater Interfaces, 2014, 6: 4196-4206 CrossRef PubMed Google Scholar

[15] Wang H, Xu Z, Li Z, et al. Hybrid device employing three-dimensional arrays of MnO in carbon nanosheets bridges battery-supercapacitor divide. Nano Lett, 2014, 14: 1987-1994 CrossRef PubMed ADS Google Scholar

[16] Chang HW, Lu YR, Chen JL, et al. Nanoflaky MnO₂/functionalized carbon nanotubes for supercapacitors: an in situ X-ray absorption spectroscopic investigation. Nanoscale, 2015, 7: 1725-1735 CrossRef PubMed ADS Google Scholar

[17] Zhang Z, Chi K, Xiao F, et al. Advanced solid-state asymmetric supercapacitors based on 3D graphene/MnO₂ and graphene/polypyrrole hybrid architectures. J Mater Chem A, 2015, 3: 12828-12835 CrossRef Google Scholar

[18] Zhong J, Zhang Y, Zhong Q, et al. Fiber-based generator for wearable electronics and mobile medication. ACS Nano, 2014, 8: 6273-6280 CrossRef PubMed Google Scholar

[19] Xie B, Yang C, Zhang Z, et al. Shape-tailorable graphene-based ultra-high-rate supercapacitor for wearable electronics. ACS Nano, 2015, 9: 5636-5645 CrossRef Google Scholar

[20] Huang Y, Hu H, Huang Y, et al. From industrially weavable and knittable highly conductive yarns to large wearable energy storage textiles. ACS Nano, 2015, 9: 4766-4775 CrossRef Google Scholar

[21] Zhang X, Zhang H, Lin Z, et al. Recent advances and challenges of stretchable supercapacitors based on carbon materials. Sci China Mater, 2016, 59: 475-494 CrossRef Google Scholar

[22] Yu M, Cheng X, Zeng Y, et al. Dual-doped molybdenum trioxide nanowires: a bifunctional anode for fiber-shaped asymmetric supercapacitors and microbial fuel cells. Angew Chem Int Ed, 2016, 55: 6762-6766 CrossRef PubMed Google Scholar

[23] Yu M, Zhao S, Feng H, et al. Engineering thin MoS₂ nanosheets on TiN nanorods: advanced electrochemical capacitor electrode and hydrogen evolution electrocatalyst. ACS Energy Lett, 2017, 2: 1862-1868 CrossRef Google Scholar

[24] Dong X, Chen L, Su X, et al. Flexible aqueous lithium-ion battery with high safety and large volumetric energy density. Angew Chem Int Ed, 2016, 55: 7474-7477 CrossRef PubMed Google Scholar

[25] Zeng Y, Zhang X, Meng Y, et al. Achieving ultrahigh energy density and long durability in a flexible rechargeable quasi-solid-state Zn-MnO₂ battery. Adv Mater, 2017, 29: 1700274-1700281 CrossRef PubMed Google Scholar

[26] Wang Z, Carlsson DO, Tammela P, et al. Surface modified nanocellulose fibers yield conducting polymer-based flexible supercapacitors with enhanced capacitances. ACS Nano, 2015, 9: 7563-7571 CrossRef Google Scholar

[27] Dong L, Xu C, Yang Q, et al. High-performance compressible supercapacitors based on functionally synergic multiscale carbon composite textiles. J Mater Chem A, 2015, 3: 4729-4737 CrossRef Google Scholar

[28] Wang X, Liu B, Liu R, et al. Fiber-based flexible all-solid-state asymmetric supercapacitors for integrated photodetecting system. Angew Chem Int Ed, 2014, 53: 1849-1853 CrossRef PubMed Google Scholar

[29] Wang Q, Wang X, Xu J, et al. Flexible coaxial-type fiber supercapacitor based on NiCo₂O₄ nanosheets electrodes. Nano Energy, 2014, 8: 44-51 CrossRef Google Scholar

[30] Yu D, Qian Q, Wei L, et al. Emergence of fiber supercapacitors. Chem Soc Rev, 2015, 44: 647-662 CrossRef PubMed Google Scholar

[31] Xu H, Hu X, Sun Y, et al. Flexible fiber-shaped supercapacitors based on hierarchically nanostructured composite electrodes. Nano Res, 2014, 8: 1148-1158 CrossRef Google Scholar

[32] Meng Y, Zhao Y, Hu C, et al. All-graphene core-sheath microfibers for all-solid-state, stretchable fibriform supercapacitors and wearable electronic textiles. Adv Mater, 2013, 25: 2326-2331 CrossRef PubMed Google Scholar

[33] Shao Y, El-Kady MF, Wang LJ, et al. Graphene-based materials for flexible supercapacitors. Chem Soc Rev, 2015, 44: 3639-3665 CrossRef PubMed Google Scholar

[34] Zhao C, Shu K, Wang C, et al. Reduced graphene oxide and polypyrrole/reduced graphene oxide composite coated stretchable fabric electrodes for supercapacitor application. Electrochim Acta, 2015, 172: 12-19 CrossRef Google Scholar

[35] He Y, Chen W, Li X, et al. Freestanding three-dimensional graphene/MnO₂ composite networks as ultralight and flexible supercapacitor electrodes. ACS Nano, 2013, 7: 174-182 CrossRef PubMed Google Scholar

[36] Zhang Z, Xiao F, Wang S. Hierarchically structured MnO₂/graphene/carbon fiber and porous graphene hydrogel wrapped copper wire for fiber-based flexible all-solid-state asymmetric supercapacitors. J Mater Chem A, 2015, 3: 11215-11223 CrossRef Google Scholar

[37] Zhu J, He J. Facile synthesis of graphene-wrapped honeycomb MnO₂ nanospheres and their application in supercapacitors. ACS Appl Mater Interfaces, 2012, 4: 1770-1776 CrossRef PubMed Google Scholar

[38] Lai L, Yang H, Wang L, et al. Preparation of supercapacitor electrodes through selection of graphene surface functionalities. ACS Nano, 2012, 6: 5941-5951 CrossRef PubMed Google Scholar

[39] Feng X, Zhou J, Wang L, et al. Synthesis of shape-controlled NiO-graphene nanocomposites with enhanced supercapacitive properties. New J Chem, 2015, 39: 4026-4034 CrossRef Google Scholar

[40] Lai F, Miao YE, Huang Y, et al. Flexible hybrid membranes of NiCo₂O₄-doped carbon nanofiber@MnO₂ core-sheath nanostructures for high-performance supercapacitors. J Phys Chem C, 2015, 119: 13442-13450 CrossRef Google Scholar

[41] Xie Y, Xia C, Du H, et al. Enhanced electrochemical performance of polyaniline/carbon/titanium nitride nanowire array for flexible supercapacitor. J Power Sources, 2015, 286: 561-570 CrossRef ADS Google Scholar

[42] Buller S, Karden E, Kok D, et al. Modeling the dynamic behavior of supercapacitors using impedance spectroscopy. In: Thirty-Sixth IAS Annual Meeting. Conference Record of the 2001 IEEE, 2001, 4: 2500–2504. Google Scholar

[43] Barcellona S, Piegari L. A lithium-ion capacitor model working on a wide temperature range. J Power Sources, 2017, 342: 241-251 CrossRef ADS Google Scholar

[44] Kaempgen M, Chan CK, Ma J, et al. Printable thin film supercapacitors using single-walled carbon nanotubes. Nano Lett, 2009, 9: 1872-1876 CrossRef PubMed ADS Google Scholar

[45] Kang YJ, Chung H, Han CH, et al. All-solid-state flexible supercapacitors based on papers coated with carbon nanotubes and ionic-liquid-based gel electrolytes. Nanotechnology, 2012, 23: 065401 CrossRef PubMed ADS Google Scholar

[46] Bae J, Song MK, Park YJ, et al. Fiber supercapacitors made of nanowire-fiber hybrid structures for wearable/flexible energy storage. Angew Chem Int Ed, 2011, 50: 1683-1687 CrossRef PubMed Google Scholar

[47] Ren J, Bai W, Guan G, et al. Flexible and weaveable capacitor wire based on a carbon nanocomposite fiber. Adv Mater, 2013, 25: 5965-5970 CrossRef PubMed Google Scholar

[48] Yuan L, Lu XH, Xiao X, et al. Flexible solid-state supercapacitors based on carbon nanoparticles/MnO₂ nanorods hybrid structure. ACS Nano, 2011, 6: 656-661 CrossRef PubMed Google Scholar

[49] Pandey GP, Rastogi AC, Westgate CR. All-solid-state supercapacitors with poly(3,4-ethylenedioxythiophene)-coated carbon fiber paper electrodes and ionic liquid gel polymer electrolyte. J Power Sources, 2014, 245: 857-865 CrossRef ADS Google Scholar

[50] Yu P, Li Y, Zhao X, et al. Graphene-wrapped polyaniline nanowire arrays on nitrogen-doped carbon fabric as novel flexible hybrid electrode materials for high-performance supercapacitor. Langmuir, 2014, 30: 5306-5313 CrossRef PubMed Google Scholar

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Figure 1
Schematic illustration for the fabrication process of Ni@rGO@MnO₂ FE via electrochemical deposition and the symmetrical FSC composed of two Ni@rGO@MnO₂ FEs.
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Figure 2
SEM images of Ni@rGO FE (a, b), Ni@rGO@MnO₂ FE (c, d), TEM images of rGO peeled from Ni@rGO FE (e) and MnO₂/rGO peeled from Ni@rGO@MnO₂ FE (f).
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Figure 3
(a) FTIR spectra of GO, rGO and MnO₂/rGO; (b) XRD pattern of MnO₂/rGO.
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Figure 4
XPS spectra survey scan of GO and MnO₂/rGO (a), C 1s of GO and MnO₂/rGO (b), Mn 2p of MnO₂/rGO (c).
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Figure 5
CV curves (a) and corresponding specific capacitances (b) of Ni@rGO@MnO₂ FE at different scan rates in 1?mol?L^?1 Na₂SO₄; GCD curves (c) and corresponding specific capacitances (d) of Ni@rGO@MnO₂ FE at different current densities in 1?mol?L^?1 Na₂SO₄.
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Figure 6
CV curves (a) and corresponding specific capacitances (b) of symmetrical fiber-shaped Ni@rGO@MnO₂ FSC at different scan rates; GCD curves (c) and corresponding specific capacitances (d) of symmetrical fiber-shaped Ni@rGO@MnO₂ FSC at different current densities.
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Figure 7
(a) Ragone plots of symmetrical fiber-shaped Ni@rGO@MnO₂ FSC and the comparison with the previous FSCs; (b) capacitance retention after 3000 charge-discharge cycles at a current density of 1?mA?cm^?2 (inset: optical photo shows that two devices in series light a LED).
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Figure 8
The CV curves of the symmetric fiber-shaped Ni@rGO@MnO₂ FSC device at 100 mV s^?1 with different bending angles (a) and bending cycle numbers (b). GCD curves of a single FSC (black lines) and two FSCs (red lines) connected in series (c) and in parallel (d).