Abstract
Transitional metal oxides are demonstrated as promising candidates for pseudocapacitive electrode materials for use in high-performance supercapacitors. Here, we report a rational design of the MnO2@NiO nanosheets@nanowires hybrid structure. The as-prepared hierarchical structure shows highly uniformity and interconnection between ultrathin MnO2 nanosheets and NiO nanowires. The well-designed MnO2@NiO is directly used as binder-free electrode and exhibits a high specific capacitance (374.6 F g−1 at a current density of 0.25 A g−1; areal capacitance of 1.3 F cm−2), good rate capability, and excellent cycling stability (92.7% capacitance retention after 5000 charge/discharge cycles). An asymmetric supercapacitor (ASC) is assembled using the MnO2@NiO as the positive electrode and activated microwave exfoliated graphite oxide as the negative electrode. The assembled ASC shows excellent electrochemical performance with an energy density of 15.4 W kg−1 and a maximum power density of 9360 W kg−1. These analytical and experimental results clearly indicate the advantages of multicomponent hierarchical core–shell structure for engineering high-performance electrochemical capacitors.
Similar content being viewed by others
References
Miller JR, Simon P (2008) Electrochemical capacitors for energy management. Science 321:651–652
Wang G, Zhang L, Zhang J (2012) A review of electrode materials for electrochemical supercapacitors. Chem Soc Rev 41:797–828
Huang M, Li F, Dong F, Zhang YX, Zhang LL (2015) MnO2-based nanostructures for high-performance supercapacitors. J Mater Chem A 3:21380–21423
Wang J, Li F, Zhu F, Schmidt OG (2018) Recent progress in micro-supercapacitor design, integration, and functionalization. Small Methods 3:1800367
Yu Z, Tetard L, Zhai L, Thomas J (2015) Supercapacitor electrode materials: nanostructures from 0 to 3 dimensions. Energ Environ Sci 8:702–730
Ji J, Zhang LL, Ji H, Li Y, Zhao X, Bai X, Fan X, Zhang F, Ruoff RS (2013) Nanoporous Ni(OH)2 thin film on 3D ultrathin-graphite foam for asymmetric supercapacitor. ACS Nano 7:6237–6243
Zhang LL, Zhao X (2009) Carbon-based materials as supercapacitor electrodes. Chem Soc Rev 38:2520–2531
Zhang LL, Zhou R, Zhao X (2010) Graphene-based materials as supercapacitor electrodes. J Mater Chem 20:5983–5992
Li H, Wu X, Zhou J, Liu Y, Huang M, Xing W, Yan Z, Zhuo S (2019) Enhanced supercapacitive performance of MnCO3@rGO in an electrolyte with KI as additive. ChemElectroChem 6:316–319
Wu ZS, Wang DW, Ren W, Zhao J, Zhou G, Li F, Cheng HM (2010) Anchoring hydrous RuO2 on graphene sheets for high-performance electrochemical capacitors. Adv Funct Mater 20:3595–3602
Huang M, Zhao XL, Li F, Li W, Zhang B, Zhang YX (2015) Synthesis of Co3O4/SnO2@MnO2 core–shell nanostructures for high-performance supercapacitors. J Mater Chem A 3:12852–12857
Huang M, Li F, Ji JY, Zhang YX, Zhao XL, Gao X (2014) Facile synthesis of single-crystalline NiO nanosheet arrays on Ni foam for high-performance supercapacitors. CrystEngComm 16:2878–2884
Yao B, Chandrasekaran S, Zhang J, Xiao W, Qian F, Zhu C, Duoss EB, Spadaccini CM, Worsley MA, Li Y (2019) Efficient 3D printed pseudocapacitive electrodes with ultrahigh MnO2 loading. Joule 3:459–470
Xu W, Dai S, Liu G, Xi Y, Hu C, Wang X (2016) CuO nanoflowers growing on carbon fiber fabric for flexible high-performance supercapacitors. Electrochim Acta 203:1–8
Huang M, Zhao XL, Li F, Zhang LL, Zhang YX (2015) Facile synthesis of ultrathin manganese dioxide nanosheets arrays on nickel foam as advanced binder-free supercapacitor electrodes. J Power Sources 277:36–43
Huang M, Mi R, Liu H, Li F, Zhao XL, Zhang W, He SX, Zhang YX (2014) Layered manganese oxides-decorated and nickel foam-supported carbon nanotubes as advanced binder-free supercapacitor electrodes. J Power Sources 269:760–767
Toupin M, Brousse T, Bélanger D (2004) Charge storage mechanism of MnO2 electrode used in aqueous electrochemical capacitor. Chem Mater 16:3184–3190
Huang Z-H, Song Y, Feng D-Y, Sun Z, Sun X, Liu X-X (2018) High mass loading MnO2 with hierarchical nanostructures for supercapacitors. ACS Nano 12:3557–3567
Li Q, Wang Z-L, Li G-R, Guo R, Ding L-X, Tong Y-X (2012) Design and synthesis of MnO2/Mn/MnO2 sandwich-structured nanotube arrays with high supercapacitive performance for electrochemical energy storage. Nano Lett 12:3803–3807
Wu Z-S, Ren W, Wang D-W, Li F, Liu B, Cheng H-M (2010) High-energy MnO2 nanowire/graphene and graphene asymmetric electrochemical capacitors. ACS Nano 4:5835–5842
Li F, Xing Y, Huang M, Li KL, Yu TT, Zhang YX, Losic D (2015) MnO2 nanostructures with three-dimensional (3D) morphology replicated from diatoms for high-performance supercapacitors. J Mater Chem A 3:7855–7861
Le QJ, Huang M, Wang T, Liu XY, Sun L, Guo XL, Jiang DB, Wang J, Dong F, Zhang YX (2019) Biotemplate derived three dimensional nitrogen doped graphene@ MnO2 as bifunctional material for supercapacitor and oxygen reduction reaction catalyst. J Colloid Interface Sci 544:155–163
Qi H, Bo Z, Yang S, Duan L, Yang H, Yan J, Cen K, Ostrikov KK (2019) Hierarchical nanocarbon-MnO2 electrodes for enhanced electrochemical capacitor performance. Energy Storage Mater 16:607–618
Lv X, Zhang H, Wang F, Hu Z, Zhang Y, Zhang L, Xie R, Ji J (2018) Controllable synthesis of MnO2 nanostructures anchored on graphite foam with different morphologies for a high-performance asymmetric supercapacitor. CrystEngComm 20:1690–1697
Liu J, Jiang J, Bosman M, Fan HJ (2012) Three-dimensional tubular arrays of MnO2–NiO nanoflakes with high areal pseudocapacitance. J Mater Chem 22:2419–2426
Zhang X, Yu P, Zhang H, Zhang D, Sun X, Ma Y (2013) Rapid hydrothermal synthesis of hierarchical nanostructures assembled from ultrathin birnessite-type MnO2 nanosheets for supercapacitor applications. Electrochim Acta 89:523–529
Soriano L, Preda I, Gutiérrez A, Palacín S, Abbate M, Vollmer A (2007) Surface effects in the Ni2p x-ray photoemission spectra of NiO. Phys Rev B 75:233417
Preda I, Gutiérrez A, Abbate M, Yubero F, Méndez J, Alvarez L, Soriano L (2008) Interface effects in the Ni2p x-ray photoelectron spectra of NiO thin films grown on oxide substrates. Phys Rev B 77:075411
Chen J, Huang Y, Li C, Chen X, Zhang X (2016) Synthesis of NiO@MnO2 core/shell nanocomposites for supercapacitor application. Appl Surf Sci 360:534–539
Chao D, Zhou W, Ye C, Zhang Q, Chen Y, Gu L, Davey K, Qiao SZ (2019) An electrolytic Zn–MnO2 battery for high-voltage and scalable energy storage. Angew Chem Int Ed 58:7823–7828
Yu G, Hu L, Vosgueritchian M, Wang H, Xie X, McDonough JR, Cui X, Cui Y, Bao Z (2011) Solution-processed graphene/MnO2 nanostructured textiles for high-performance electrochemical capacitors. Nano Lett 11:2905–2911
Deng L, Zhu G, Wang J, Kang L, Liu Z-H, Yang Z, Wang Z (2011) Graphene–MnO2 and graphene asymmetrical electrochemical capacitor with a high energy density in aqueous electrolyte. J Power Sources 196:10782–10787
Zhang S, Yin B, Wang Z, Peter F (2016) Super long-life all solid-state asymmetric supercapacitor based on NiO nanosheets and α-Fe2O3 nanorods. Chem Eng J 306:193–203
Xu W, Mu B, Wang A (2016) Facile fabrication of well-defined microtubular carbonized kapok fiber/NiO composites as electrode material for supercapacitor. Electrochim Acta 194:84–94
Acknowledgements
The financial support funded by Chongqing Special Postdoctoral Science Foundation (XmT2018043) was highly appreciated. FL acknowledges the support and funding from China Scholarship Council (CSC).
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Conflict of interest
All authors listed have declared that they have no conflict of interest.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Zhao, X., Liu, X., Li, F. et al. MnO2@NiO nanosheets@nanowires hierarchical structures with enhanced supercapacitive properties. J Mater Sci 55, 2482–2491 (2020). https://doi.org/10.1007/s10853-019-04112-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10853-019-04112-4