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Solid-state yet flexible supercapacitors made by inkjet-printing hybrid ink of carbon quantum dots/graphene oxide platelets on paper

喷墨打印碳量子点/氧化石墨烯混合墨水制备纸基全固态柔性超级电容器

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Abstract

Paper-based flexible supercapacitors (SCs) show advantages due to the improved adhesion between paper and active materials, the simplified printing process and the lower cost, compared to other substrates such as plastics. Here we report the fabrication of solid-state yet flexible SCs by inkjetprinting a hybrid ink consisting of carbon quantum dots (CQDs) and graphene oxide (GO) platelets, followed by casting of polyvinyl alcohol (PVA)/sulfuric acid (H2SO4) gel electrolyte. The SC obtained from 100-time-printing of the hybrid ink shows a specific capacitance of ~1.0 mF cm−2 at a scan rate of 100 mV s−1, which is enhanced by nearly 150%; the whole device including paper substrate, gel electrolyte and active material demonstrates an energy density of 0.078 mW h cm−3 at a power density of 0.28 mW cm−3. In addition, the excellent mechanical strength of GO platelets ensures the good flexibility and mechanical robustness of the printed SCs, which show a retention of 98% in capacitance after being bended for 1,000 cycles at a bending radius of 7.6 mm. This study demonstrates a promising strategy for the large-scale preparation of low-cost, lightweight, and flexible/wearable energy storage devices based on carbon-based ink and paper substrate.

摘要

与其他柔性基底材料如塑料相比, 纸基柔性超级电容器具有印刷工艺简单、 制造价格低廉以及基底和活性材料之间具有更好的粘合力等优势. 在这里, 我们通过喷墨打印碳量子点(CQDs)和氧化石墨烯(GO)组成的混合墨水、 采用PVA/H2SO4为凝胶电解质制备了固态柔性超级电容器, 并对其性能进行了系统研究. 打印100次混合墨水获得的超级电容器在100 mV s−1的扫描速率下显示出~1.0 mF cm−2的比电容, 相比于纯GO墨水制备的超级电容器其比电容增加了150%; 通过进一步优化, 基于超级电容器整个装置(包括纸基、 凝胶电解质和活性材料)在0.28 mW cm−3的功率密度下表现出0.078 mW h cm−3的能量密度. 此外, GO薄片具有出色的机械强度, 确保超级电容器具有良好的柔韧性和机械强度, 在弯曲半径为7.6 mm的条件下弯曲1000次后, 仍保留98%的电容. 基于碳基墨水和纸张基材的喷墨打印的技术为低成本、 轻便、 灵活/可穿戴式储能装置的大规模制备提供了可能.

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References

  1. 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

    Article  Google Scholar 

  2. Peng L, Zhu Y, Li H, et al. Chemically integrated inorganic-graphene two-dimensional hybrid materials for flexible energy storage devices. Small, 2016, 12: 6183–6199

    Article  Google Scholar 

  3. Ye J, Tan H, Wu S, et al. Direct laser writing of graphene made from chemical vapor deposition for flexible, integratable microsupercapacitors with ultrahigh power output. Adv Mater, 2018, 26: 1801384

    Article  Google Scholar 

  4. Simon P, Gogotsi Y. Materials for electrochemical capacitors. Nat Mater, 2008, 7: 845–854

    Article  Google Scholar 

  5. 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

    Article  Google Scholar 

  6. Bonaccorso F, Colombo L, Yu G, et al. Graphene, related twodimensional crystals, and hybrid systems for energy conversion and storage. Science, 2015, 347: 1246501–1246501

    Article  Google Scholar 

  7. Xiao X, Li T, Yang P, et al. Fiber-based all-solid-state flexible supercapacitors for self-powered systems. ACS Nano, 2012, 6: 9200–9206

    Article  Google Scholar 

  8. Huang C, Grant PS. One-step spray processing of high power allsolid-state supercapacitors. Sci Rep, 2013, 3: 2393

    Article  Google Scholar 

  9. Zhang X, Lin Z, Chen B, et al. Solid-state, flexible, high strength paper-based supercapacitors. J Mater Chem A, 2013, 1: 5835–5839

    Article  Google Scholar 

  10. Hu L, Pasta M, La Mantia F, et al. Stretchable, porous, and conductive energy textiles. Nano Lett, 2010, 10: 708–714

    Article  Google Scholar 

  11. Kang YJ, Chun SJ, Lee SS, et al. All-solid-state flexible supercapacitors fabricated with bacterial nanocellulose papers, carbon nanotubes, and triblock-copolymer ion gels. ACS Nano, 2012, 6: 6400–6406

    Article  Google Scholar 

  12. Zheng G, Hu L, Wu H, et al. Paper supercapacitors by a solventfree drawing method. Energy Environ Sci, 2011, 4: 3368

    Article  Google Scholar 

  13. Wang Y, Shi Y, Zhao CX, et al. Printed all-solid flexible microsupercapacitors: towards the general route for high energy storage devices. Nanotechnology, 2014, 25: 094010

    Article  Google Scholar 

  14. Liu Z, Wu ZS, Yang S, et al. Ultraflexible in-plane micro-supercapacitors by direct printing of solution-processable electrochemically exfoliated graphene. Adv Mater, 2016, 28: 2217–2222

    Article  Google Scholar 

  15. Kamyshny A, Magdassi S. Conductive nanomaterials for printed electronics. Small, 2014, 10: 3515–3535

    Article  Google Scholar 

  16. Song JW, Kim J, Yoon YH, et al. Inkjet printing of single-walled carbon nanotubes and electrical characterization of the line pattern. Nanotechnology, 2008, 19: 095702

    Article  Google Scholar 

  17. Liu W, Lu C, Li H, et al. Paper-based all-solid-state flexible microsupercapacitors with ultra-high rate and rapid frequency response capabilities. J Mater Chem A, 2016, 4: 3754–3764

    Article  Google Scholar 

  18. Chen P, Chen H, Qiu J, et al. Inkjet printing of single-walled carbon nanotube/RuO2 nanowire supercapacitors on cloth fabrics and flexible substrates. Nano Res, 2010, 3: 594–603

    Article  Google Scholar 

  19. Hu L, Choi JW, Yang Y, et al. Highly conductive paper for energystorage devices. Proc Natl Acad Sci USA, 2009, 106: 21490–21494

    Article  Google Scholar 

  20. de Gans BJ, Duineveld P, Schubert U. Inkjet printing of polymers: state of the art and future developments. Adv Mater, 2004, 16: 203–213

    Article  Google Scholar 

  21. Le L, Ervin M, Qiu H, et al. In Inkjet-printed graphene for flexible micro-supercapacitors. Nanotechnology, 2011, 67–71

    Google Scholar 

  22. Xu Y, Hennig I, Freyberg D, et al. Inkjet-printed energy storage device using graphene/polyaniline inks. J Power Sources, 2014, 248: 483–488

    Article  Google Scholar 

  23. Wang S, Liu N, Tao J, et al. Inkjet printing of conductive patterns and supercapacitors using a multi-walled carbon nanotube/Ag nanoparticle based ink. J Mater Chem A, 2015, 3: 2407–2413

    Article  Google Scholar 

  24. Zhang LL, Zhao X, Stoller MD, et al. Highly conductive and porous activated reduced graphene oxide films for high-power supercapacitors. Nano Lett, 2012, 12: 1806–1812

    Article  Google Scholar 

  25. Gao W, Singh N, Song L, et al. Direct laser writing of microsupercapacitors on hydrated graphite oxide films. Nat Nanotech, 2011, 6: 496–500

    Article  Google Scholar 

  26. Li P, Jin Z, Peng L, et al. Stretchable all-gel-state fiber-shaped supercapacitors enabled by macromolecularly interconnected 3D graphene/nanostructured conductive polymer hydrogels. Adv Mater, 2018, 30: 1800124

    Article  Google Scholar 

  27. Peng L, Fang Z, Zhu Y, et al. Holey 2D nanomaterials for electrochemical energy storage. Adv Energy Mater, 2018, 8: 1702179

    Article  Google Scholar 

  28. Pei Z, Hu H, Liang G, et al. Carbon-based flexible and all-solidstate micro-supercapacitors fabricated by inkjet printing with enhanced performance. Nano-Micro Lett, 2017, 9: 19

    Article  Google Scholar 

  29. Jiang L, Sheng L, Long C, et al. Functional pillared graphene frameworks for ultrahigh volumetric performance supercapacitors. Adv Energy Mater, 2015, 5: 1500771

    Article  Google Scholar 

  30. Byon HR, Gallant BM, Lee SW, et al. Role of oxygen functional groups in carbon nanotube/graphene freestanding electrodes for high performance lithium batteries. Adv Funct Mater, 2013, 23: 1037–1045

    Article  Google Scholar 

  31. Zhao X, Li M, Dong H, et al. Interconnected 3 D network of graphene-oxide nanosheets decorated with carbon dots for highperformance supercapacitors. ChemSusChem, 2017, 10: 2626–2634

    Article  Google Scholar 

  32. Chen G, Wu S, Hui L, et al. Assembling carbon quantum dots to a layered carbon for high-density supercapacitor electrodes. Sci Rep, 2016, 6: 19028

    Article  Google Scholar 

  33. Lin L, Zhang S. Creating high yield water soluble luminescent graphene quantum dots via exfoliating and disintegrating carbon nanotubes and graphite flakes. Chem Commun, 2012, 48: 10177–10179

    Article  Google Scholar 

  34. Mei Q, Zhang K, Guan G, et al. Highly efficient photoluminescent graphene oxide with tunable surface properties. Chem Commun, 2010, 46: 7319–7321

    Article  Google Scholar 

  35. Miller JR, Outlaw RA, Holloway BC. Graphene electric double layer capacitor with ultra-high-power performance. Electrochim Acta, 2011, 56: 10443–10449

    Article  Google Scholar 

  36. Zhu Y, Peng L, Fang Z, et al. Structural engineering of 2D nanomaterials for energy storage and catalysis. Adv Mater, 2018, 30: 1706347

    Article  Google Scholar 

  37. Raymundo-Piñero E, Cadek M, Béguin F. Tuning carbon materials for supercapacitors by direct pyrolysis of seaweeds. Adv Funct Mater, 2009, 19: 1032–1039

    Article  Google Scholar 

  38. Zhao B, Liu P, Jiang Y, et al. Supercapacitor performances of thermally reduced graphene oxide. J Power Sources, 2012, 198: 423–427

    Article  Google Scholar 

  39. Fang Y, Luo B, Jia Y, et al. Renewing functionalized graphene as electrodes for high-performance supercapacitors. Adv Mater, 2012, 24: 6348–6355

    Article  Google Scholar 

  40. Li L, Li F. The effect of carbonyl, carboxyl and hydroxyl groups on the capacitance of carbon nanotubes. New Carbon Mater, 2011, 26: 224–228

    Article  Google Scholar 

  41. Yan Y, Kuila T, Kim NH, et al. Effects of acid vapour mediated oxidization on the electrochemical performance of thermally exfoliated graphene. Carbon, 2014, 74: 195–206

    Article  Google Scholar 

  42. Hulicova-Jurcakova D, Seredych M, Lu GQ, et al. Combined effect of nitrogen- and oxygen-containing functional groups of microporous activated carbon on its electrochemical performance in supercapacitors. Adv Funct Mater, 2009, 19: 438–447

    Article  Google Scholar 

  43. Yang F, Zhao M, Zheng B, et al. Influence of pH on the fluorescence properties of graphene quantum dots using ozonation preoxide hydrothermal synthesis. J Mater Chem, 2012, 22: 25471–25479

    Article  Google Scholar 

  44. Bagri A, Mattevi C, Acik M, et al. Structural evolution during the reduction of chemically derived graphene oxide. Nat Chem, 2010, 2: 581–587

    Article  Google Scholar 

  45. Xiao X, Li T, Peng Z, et al. Freestanding functionalized carbon nanotube-based electrode for solid-state asymmetric supercapacitors. Nano Energy, 2014, 6: 1–9

    Article  Google Scholar 

  46. Gao K, Shao Z, Wu X, et al. Paper-based transparent flexible thin film supercapacitors. Nanoscale, 2013, 5: 5307–5311

    Article  Google Scholar 

  47. Cheng Y, Lu S, Zhang H, et al. Synergistic effects from graphene and carbon nanotubes enable flexible and robust electrodes for high-performance supercapacitors. Nano Lett, 2012, 12: 4206–4211

    Article  Google Scholar 

  48. Kim MS, Hsia B, Carraro C, et al. Flexible micro-supercapacitors with high energy density from simple transfer of photoresist-derived porous carbon electrodes. Carbon, 2014, 74: 163–169

    Article  Google Scholar 

  49. Liu S, Xie J, Li H, et al. Nitrogen-doped reduced graphene oxide for high-performance flexible all-solid-state micro-supercapacitors. J Mater Chem A, 2014, 2: 18125–18131

    Article  Google Scholar 

  50. Kaempgen M, Chan CK, Ma J, et al. Printable thin film supercapacitors using single-walled carbon nanotubes. Nano Lett, 2009, 9: 1872–1876

    Article  Google Scholar 

  51. Zheng H, Zhai T, Yu M, et al. TiO2@C core–shell nanowires for high-performance and flexible solid-state supercapacitors. J Mater Chem C, 2013, 1: 225–229

    Article  Google Scholar 

  52. Yang P, Xiao X, Li Y, et al. Hydrogenated ZnO core–shell nanocables for flexible supercapacitors and self-powered systems. ACS Nano, 2013, 7: 2617–2626

    Article  Google Scholar 

  53. Lu X, Wang G, Zhai T, et al. Stabilized TiN nanowire arrays for high-performance and flexible supercapacitors. Nano Lett, 2012, 12: 5376–5381

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the Thousand Talents Plan of China, the Program for New Century Excellent Talents in University, and the National Natural Science Foundation of China (51322204 and 51772282).

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Authors and Affiliations

  1. Key Laboratory of Materials for Energy Conversion, Chinese Academy of Sciences, & Department of Materials Science and Engineering, University of Science and Technology of China, Hefei, 230026, China

    Jie Liu  (刘杰), Jianglin Ye  (叶江林), Fei Pan  (潘飞), Xiangyang Wang  (王向阳) & Yanwu Zhu  (朱彦武)

  2. iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), University of Science and Technology of China, Hefei, 230026, China

    Yanwu Zhu  (朱彦武)

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  1. Jie Liu  (刘杰)
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  2. Jianglin Ye  (叶江林)
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  3. Fei Pan  (潘飞)
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  4. Xiangyang Wang  (王向阳)
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  5. Yanwu Zhu  (朱彦武)
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Corresponding author

Correspondence to Yanwu Zhu  (朱彦武).

Additional information

Jie Liu is a graduate student at the University of Science and Technology of China. She is currently studying in the Department of Materials Science and Engineering. Her research focuses on the energy storage of new carbon-based composites.

Yanwu Zhu is currently a Professor of the Department of Materials Science and Engineering, University of Science and Technology of China. He obtained a BSc degree in applied physics from the National University of Defense Technology in 2000, a MSc degree in physics from Peking University in 2003, and a PhD degree in physics from the National University of Singapore in 2007. He was a postdoctoral researcher at the National University of Singapore and at the University of Texas at Austin. In the last decade, he has been engaged in the preparation, characterization and property research of graphene and other novel carbon materials.

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Solid-state yet flexible supercapacitors made by inkjet-printing hybrid ink of carbon quantum dots/graphene oxide platelets on paper

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Liu, J., Ye, J., Pan, F. et al. Solid-state yet flexible supercapacitors made by inkjet-printing hybrid ink of carbon quantum dots/graphene oxide platelets on paper. Sci. China Mater. 62, 545–554 (2019). https://doi.org/10.1007/s40843-018-9309-x

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