Micro-supercapacitors (MSCs) have emerged as one competitive candidate of high-performance, flexible, safe, portable and wearable energy storage devices. However, improving their electrochemical performance from electrode materials to assembled devices still remains huge challenges. Here, we for the first time synthesized two-dimensional (2D), ultrathin, mesoporous polypyrrole-based graphene nanosheets uniformly anchored with redox polyoxometalate (mPPy@rGO-POM) by soft template approach. Further, using a layer-by-layer deposition and mask-assisted technique, the compactly stacked and sandwich-like hybrid film (mPGM) based on pseudocapacitive mPPy@rGO-POM nanosheets and electrochemically exfoliated graphene was directly fabricated as binder- and additive-free interdigital electrodes for all-solid-state planar micro-supercapacitors (mPGM-MSCs). Notably, the resulted mPGM-MSCs exhibited outstanding areal capacitance (115 mF cm–2), remarkably enhanced volumetric capacitance (137 F cm–3 at 1 mV s–1) in comparison with MSCs based on the films of mPPy@rGO without POM anchoring (95 F cm–3), and non-porous polypyrrole-graphene (68 F cm–3). Further, mPGM-MSCs disclosed robust mechanical flexibility with ~96% of capacitance retention at a highly bending angle of 180°, and impressive parallel or serial interconnection for boosting capacitance or voltage output. As a consequence, our proposed strategy of filling the redox species into mesoporous graphene and other 2D nanosheets will open up new ways to manufacture high-compact and flexible energy storage devices ranging from supercapacitors to batteries.
China Postdoctoral Science Foundation(2016M601348)
the National Natural Science Foundation of China(51572259)
and Exploratory Research Program of Shaanxi Yanchang Petroleum(Group)
National Key R&D Program of China(2016YBF0100100)
Natural Science Foundation of Liaoning Province(201602737)
Recruitment Program of Global Expert(1000)
LTD & DICP.
DICP
This work was supported by the National Natural Science Foundation of China (51572259), National Key R&D Program of China (2016YBF0100100 and 2016YFA0200200), Natural Science Foundation of Liaoning Province (201602737), Recruitment Program of Global Expert (1000 Talent Plan), DICP, China Postdoctoral Science Foundation (2016M601348), and Exploratory Research Program of Shaanxi Yanchang Petroleum (Group) Co., LTD & DICP.
The authors declare that they have no conflict of interest.
Wu ZS proposed and supervised the whole project. Qin J and Ren R conducted the experiments and prepared the MSCs. Zhou F and Xiao H participated in synthesis of EG materials and fabrication of MSCs mask. Qin J and Wu ZS wrote and revised the manuscript. All authors contributed to the discussion and comments of this manuscript.
Additional detailed calculations, and figures are available in the online version of the paper.
[1] Li W, Liu J, Zhao D. Mesoporous materials for energy conversion and storage devices. Nat Rev Mater, 2016, 1: 16023 CrossRef ADS Google Scholar
[2] Dong Y, Wu ZS, Ren W, et al. Graphene: a promising 2D material for electrochemical energy storage. Sci Bull, 2017, 62: 724-740 CrossRef Google Scholar
[3] 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
[4] Zhang X, Cheng X, Zhang Q. Nanostructured energy materials for electrochemical energy conversion and storage: a review. J Energ Chem, 2016, 25: 967-984 CrossRef Google Scholar
[5] Zhu Z, Cheng F, Hu Z, et al. Highly stable and ultrafast electrode reaction of graphite for sodium ion batteries. J Power Sources, 2015, 293: 626-634 CrossRef ADS Google Scholar
[6] Zhang C, Lv W, Tao Y, et al. Towards superior volumetric performance: design and preparation of novel carbon materials for energy storage. Energ Environ Sci, 2015, 8: 1390-1403 CrossRef Google Scholar
[7] Zheng S, Wu ZS, Wang S, et al. Graphene-based materials for high-voltage and high-energy asymmetric supercapacitors. Energ Storage Mater, 2017, 6: 70-97 CrossRef Google Scholar
[8] Wu ZS, Feng X, Cheng HM. Recent advances in graphene-based planar micro-supercapacitors for on-chip energy storage. Natl Sci Rev, 2014, 1: 277-292 CrossRef Google Scholar
[9] Liu L, Niu Z, Chen J. Unconventional supercapacitors from nanocarbon-based electrode materials to device configurations. Chem Soc Rev, 2016, 45: 4340-4363 CrossRef PubMed Google Scholar
[10] Wu ZS, Parvez K, Feng X, et al. Photolithographic fabrication of high-performance all-solid-state graphene-based planar micro-supercapacitors with different interdigital fingers. J Mater Chem A, 2014, 2: 8288-8293 CrossRef Google Scholar
[11] Wang Q, Yan J, Fan Z. Carbon materials for high volumetric performance supercapacitors: design, progress, challenges and opportunities. Energ Environ Sci, 2016, 9: 729-762 CrossRef Google Scholar
[12] Lin T, Chen IW, Liu F, et al. Nitrogen-doped mesoporous carbon of extraordinary capacitance for electrochemical energy storage. Science, 2015, 350: 1508-1513 CrossRef PubMed ADS Google Scholar
[13] Yang X, Cheng C, Wang Y, et al. Liquid-mediated dense integration of graphene materials for compact capacitive energy storage. Science, 2013, 341: 534-537 CrossRef PubMed ADS Google Scholar
[14] Su DS, Centi G. A perspective on carbon materials for future energy application. J Energ Chem, 2013, 22: 151-173 CrossRef Google Scholar
[15] Shi Y, Peng L, Ding Y, et al. Nanostructured conductive polymers for advanced energy storage. Chem Soc Rev, 2015, 44: 6684-6696 CrossRef PubMed Google Scholar
[16] Liu S, Wang F, Dong R, et al. Dual-template synthesis of 2D mesoporous polypyrrole nanosheets with controlled pore size. Adv Mater, 2016, 28: 8365-8370 CrossRef PubMed Google Scholar
[17] Liu S, Wang F, Dong R, et al. Soft-template construction of 3D macroporous polypyrrole scaffolds. Small, 2017, 13: 1604099 CrossRef PubMed Google Scholar
[18] Liu S, Gordiichuk P, Wu ZS, et al. Patterning two-dimensional free-standing surfaces with mesoporous conducting polymers. Nat Commun, 2015, 6: 8817 CrossRef PubMed ADS Google Scholar
[19] Wu ZS, Parvez K, Li S, et al. Alternating stacked graphene-conducting polymer compact films with ultrahigh areal and volumetric capacitances for high-energy micro-supercapacitors. Adv Mater, 2015, 27: 4054-4061 CrossRef PubMed Google Scholar
[20] Yang S, Feng X, Wang L, et al. Graphene-based nanosheets with a sandwich structure. Angew Chem Int Ed, 2010, 49: 4795-4799 CrossRef PubMed Google Scholar
[21] Ji Y, Huang L, Hu J, et al. Polyoxometalate-functionalized nanocarbon materials for energy conversion, energy storage and sensor systems. Energ Environ Sci, 2015, 8: 776-789 CrossRef Google Scholar
[22] Suárez-Guevara J, Ruiz V, Gómez-Romero P. Stable graphene–polyoxometalate nanomaterials for application in hybrid supercapacitors. Phys Chem Chem Phys, 2014, 16: 20411-20414 CrossRef PubMed ADS Google Scholar
[23] Genovese M, Lian K. Polyoxometalate modified pine cone biochar carbon for supercapacitor electrodes. J Mater Chem A, 2017, 5: 3939-3947 CrossRef Google Scholar
[24] Dubal DP, Suarez-Guevara J, Tonti D, et al. A high voltage solid state symmetric supercapacitor based on graphene–polyoxometalate hybrid electrodes with a hydroquinone doped hybrid gel-electrolyte. J Mater Chem A, 2015, 3: 23483-23492 CrossRef Google Scholar
[25] Chen Y, Han M, Tang Y, et al. Polypyrrole–polyoxometalate/reduced graphene oxide ternary nanohybrids for flexible, all-solid-state supercapacitors. Chem Commun, 2015, 51: 12377-12380 CrossRef PubMed Google Scholar
[26] Huang A, Yan J, Zhang H, et al. Effect of the pore length and orientation upon the electrochemical capacitive performance of ordered mesoporous carbons. J Energ Chem, 2017, 26: 121-128 CrossRef Google Scholar
[27] Zhu Y, Murali S, Cai W, et al. Graphene and graphene oxide: synthesis, properties, and applications. Adv Mater, 2010, 22: 3906-3924 CrossRef PubMed Google Scholar
[28] Wu ZS, Zhou GM, Yin LC, et al. Graphene/metal oxide composite electrode materials for energy storage. Nano Energy, 2012, 1: 107–131. Google Scholar
[29] Pei S, Cheng HM. The reduction of graphene oxide. Carbon, 2012, 50: 3210-3228 CrossRef Google Scholar
[30] Wu ZS, Sun Y, Tan YZ, et al. Three-dimensional graphene-based macro- and mesoporous frameworks for high-performance electrochemical capacitive energy storage. J Am Chem Soc, 2012, 134: 19532-19535 CrossRef PubMed Google Scholar
[31] Hu C, Zhao E, Nitta N, et al. Aqueous solutions of acidic ionic liquids for enhanced stability of polyoxometalate-carbon supercapacitor electrodes. J Power Sources, 2016, 326: 569-574 CrossRef ADS Google Scholar
[32] Ruiz V, Suárez-Guevara J, Gomez-Romero P. Hybrid electrodes based on polyoxometalate–carbon materials for electrochemical supercapacitors. Electrochem Commun, 2012, 24: 35-38 CrossRef Google Scholar
[33] Xiao H, Wu ZS, Chen L, et al. One-step device fabrication of phosphorene and graphene interdigital micro-supercapacitors with high energy density. ACS Nano, 2017, 11: 7284-7292 CrossRef Google Scholar
[34] Qin J, Wu ZS, Zhou F, et al. Simplified fabrication of high areal capacitance all-solid-state micro-supercapacitors based on graphene and MnO2 nanosheets. Chin Chem Lett, 2017, CrossRef Google Scholar
[35] Wang S, Wu ZS, Zheng S, et al. Scalable fabrication of photochemically reduced graphene-based monolithic micro-supercapacitors with superior energy and power densities. ACS Nano, 2017, 11: 4283-4291 CrossRef Google Scholar
[36] Zheng S, Li Z, Wu ZS, et al. High packing density unidirectional arrays of vertically aligned graphene with enhanced areal capacitance for high-power micro-supercapacitors. ACS Nano, 2017, 11: 4009-4016 CrossRef Google Scholar
[37] An X, Yang H, Wang Y, et al. Hydrothermal synthesis of coherent porous V2O3/carbon nanocomposites for high-performance lithium- and sodium-ion batteries. Sci China Mater, 2017, 60: 717-727 CrossRef Google Scholar
[38]
Cui
Z,
Guo
CX,
Yuan
W, et al.
[39] Chen C, Cao J, Lu Q, et al. Foldable all-solid-state supercapacitors integrated with photodetectors. Adv Funct Mater, 2017, 27: 1604639 CrossRef Google Scholar
[40] Liu L, Niu Z, Chen J. Design and integration of flexible planar micro-supercapacitors. Nano Res, 2017, 10: 1524-1544 CrossRef Google Scholar
[41] Wu ZS, Zheng Y, Zheng S, et al. Stacked-layer heterostructure films of 2D thiophene nanosheets and graphene for high-rate all-solid-state pseudocapacitors with enhanced volumetric capacitance. Adv Mater, 2017, 29: 1602960 CrossRef PubMed Google Scholar
[42] Wu ZS, Yang S, Zhang L, et al. Binder-free activated graphene compact films for all-solid-state micro-supercapacitors with high areal and volumetric capacitances. Energ Storage Mater, 2015, 1: 119-126 CrossRef Google Scholar
Figure 1
Scheme of the fabrication of mPPy@rGO-POM nanosheets.
Figure 2
Morphology and structure of mPPy@GO nanosheets. (a, b) SEM images. (c, d) TEM images. (e) AFM image (up) and corresponding height profile (down). (f) N2 adsorption-desorption isotherm and pore size distribution (inset).
Figure 3
(a, b) TEM images of mPPy@rGO nanosheets after reduction. (c, d) TEM and HRTEM images of mPPy@rGO-POM nanosheets. (e) EDX spectrum of mPPy@rGO-POM nanosheets. Cu element is derived from TEM grid used. (f) Raman spectra of mPPy@GO, mPPy@rGO and mPPy@rGO-POM nanosheets.
Figure 4
(a, b) Photographs of mPGM film taken at (a) flat and (b) bending states. (c, d) TEM and HRTEM images of EG nanosheets. (e) Cross-section schematic of sandwich-like mPGM film, showing an EG/mPPy@rGO-POM/EG structure. (f) Top-view SEM image of mPGM film. (g, h) Cross-section SEM images of mPGM film at low and high magnification. (i–m) Cross-section elemental mapping analyses of mPGM film, showing the presence of (i) C, (j) O, (k) Mo, (l) N and (m) P elements.
Figure 5
(a) CV curves tested at 10 mV s–1, (b) areal capacitance, (c) volumetric capacitance as a function of scan rate, and (d) Ragone plot of mPGM-MSCs, mPG-MSCs, and PG-MSCs. (e) CV curves and (f) Ragone plot of mPGM-MSCs based on the varying volume from 1, 2 to
Figure 6
(a) CV curves measured at 50 mV s–1 of mPGM-MSCs under different bending angles, and (b) capacitance retention as a function of bending angle of mPGM-MSCs. Insets in (b) are optical images of mPGM-MSCs taken at 0 and 180o. (c) CV curves tested at 50 mV s–1 and (d) GCD profiles obtained at
Copyright 2019 Science China Press Co., Ltd. 科学大众杂志社有限责任公司 版权所有
京ICP备18024590号-1
Download PDF
