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Fabrication of hybrid Co3O4/NiCo2O4 nanosheets sandwiched by nanoneedles for high-performance supercapacitors using a novel electrochemical ion exchange

电化学离子交换法辅助制备可用作高性能超级电容器电极的Co3O4/NiCo2O4纳米复合材料

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Abstract

Electrochemical ion exchange has been used to tailor the composition of transition metal oxides (Co3O4) electrode with enhanced capacity while maintaining its crystal structure and morphology. Specifically, Ni ions were incorporated to Co3O4 nanosheets sandwiched by nanoneedles to form Co3O4/NiCo2O4 composite. As positive electrode for supercapacitors, the Co3O4/NiCo2O4 composite presents a high areal capacitance of 3.2 F cm−2(1060 F g−1) at a current density of 5 mA cm−2 and outstanding rate capability as well as long cycle stability. Moreover, the assembled aqueous asymmetric supercapacitor based on Co3O4/NiCo2O4//carbon cloth electrodes delivers a considerable energy density of 3.0 mW h cm−3 at power density of 136 mW cm−3, and high rate capability (85% retention at a current density of 30 mA cm−2). A safety light composed of ten green LEDs in parallel was lit for ∼360 s using two identical supercapacitors in series, indicating a promising practical application.

摘要

离子交换技术被广泛用于调节过渡金属氧化物的成分, 采用该技术制备的超级电容器电极材料, 在保持其形貌的同时能增加其比容量. 本文报道了一种新颖的电化学方法辅助制备复合Co3O4/NiCo2O4纳米材料. 通过电化学离子交换, 可以将Ni2+快速引入并部分替换Co3O4纳米材料中的Co2+, 从而得到Co3O4和NiCo2O4的复合纳米材料.将其用作超级电容器正极材料, 在5 mA cm−2的电流密度下, 其面电容达到了3.2 F cm−2, 并展现出了良好的倍率性能及优异的循环稳定性. 此外, 两个串联的非对称器件(Co3O4/NiCo2O4//碳布)在充电3min后可以将10个并联的绿色LED点亮大约6 min, 展现出良好的实用性.

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References

  1. Wang G, Zhang L, Zhang J. A review of electrode materials for electrochemical supercapacitors. Chem Soc Rev, 2012, 41: 797–828

    Article  Google Scholar 

  2. Guo K, Ma Y, Li H, et al. Flexible wire-shaped supercapacitors in parallel double helix configuration with stable electrochemical properties under static/dynamic bending. Small, 2016, 12: 1024–1033

    Article  Google Scholar 

  3. Zhang S, Pan N. Supercapacitors performance evaluation. Adv Energ Mater, 2015, 5: 1401401

    Article  Google Scholar 

  4. Lee KK, Chin WS, Sow CH. Cobalt-based compounds and composites as electrode materials for high-performance electrochemical capacitors. J Mater Chem A, 2014, 2: 17212–17248

    Article  Google Scholar 

  5. Salanne M, Rotenberg B, Naoi K, et al. Efficient storage mechanisms for building better supercapacitors. Nat Energy, 2016, 1: 16070

    Article  Google Scholar 

  6. 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

    Article  Google Scholar 

  7. Cheng H, Hu C, Zhao Y, et al. Graphene fiber: a new material platform for unique applications. NPG Asia Mater, 2014, 6: e113

    Google Scholar 

  8. Qin T, Liu B, Wen Y, et al. Freestanding flexible graphene foams@ polypyrrole@MnO2 electrodes for high-performance supercapacitors. J Mater Chem A, 2016, 4: 9196–9203

    Article  Google Scholar 

  9. Candelaria SL, Uchaker E, Cao G. Comparison of surface and bulk nitrogen modification in highly porous carbon for enhanced supercapacitors. Sci China Mater, 2015, 58: 521–533

    Article  Google Scholar 

  10. 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 

  11. Zhi M, Xiang C, Li J, et al. Nanostructured carbon-metal oxide composite electrodes for supercapacitors: a review. Nanoscale, 2013, 5: 72–88

    Article  Google Scholar 

  12. Wen Y, Qin T, Wang Z, et al. Self-supported binder-free carbon fibers/MnO2 electrodes derived from disposable bamboo chopsticks for high-performance supercapacitors. J Alloys Compd, 2017, 699: 126–135

    Article  Google Scholar 

  13. Tan Q, Wang P, Liu H, et al. Hollow MOx-RuO2 (M=Co, Cu, Fe, Ni, CuNi) nanostructures as highly efficient electrodes for supercapacitors. Sci China Mater, 2016, 59: 323–336

    Article  Google Scholar 

  14. Nie Z, Wang Y, Zhang Y, et al. Multi-shelled α-Fe2O3 microspheres for high-rate supercapacitors. Sci China Mater, 2016, 59: 247–253

    Article  Google Scholar 

  15. Zhang C, Xiao J, Lv X, et al. Hierarchically porous Co3O4/C nanowire arrays derived from a metal-organic framework for high performance supercapacitors and the oxygen evolution reaction. J Mater Chem A, 2016, 4: 16516–16523

    Article  Google Scholar 

  16. Xia X, Tu J, Zhang Y, et al. Freestanding Co3O4 nanowire array for high performance supercapacitors. RSC Adv, 2012, 2: 1835–1841

    Article  Google Scholar 

  17. Zhang F, Yuan C, Lu X, et al. Facile growth of mesoporous Co3O4 nanowire arrays on Ni foam for high performance electrochemical capacitors. J Power Sources, 2012, 203: 250–256

    Article  Google Scholar 

  18. Xu W, Chen J, Yu M, et al. Sulphur-doped Co3O4 nanowires as an advanced negative electrode for high-energy asymmetric supercapacitors. J Mater Chem A, 2016, 4: 10779–10785

    Article  Google Scholar 

  19. Wen Y, Peng S, Wang Z, et al. Facile synthesis of ultrathin NiCo2S4 nano-petals inspired by blooming buds for high-performance supercapacitors. J Mater Chem A, 2017, 5: 7144–7152

    Article  Google Scholar 

  20. Yuan C, Yang L, Hou L, et al. Growth of ultrathin mesoporous Co3O4 nanosheet arrays on Ni foam for high-performance electrochemical capacitors. Energ Environ Sci, 2012, 5: 7883

    Article  Google Scholar 

  21. Jiang Y, Zhang L, Zhang H, et al. Hierarchical Ni0.54Co0.46O2 nanowire and nanosheet arrays grown on carbon fiber cloth for highperformance supercapacitors. J Power Sources, 2016, 329: 473–483

    Article  Google Scholar 

  22. Wu HB, Pang H, Lou XWD. Facile synthesis of mesoporous Ni0.3Co2.7O4 hierarchical structures for high-performance supercapacitors. Energ Environ Sci, 2013, 6: 3619

    Article  Google Scholar 

  23. Wang H, Gao Q, Jiang L. Facile approach to prepare nickel cobaltite nanowire materials for supercapacitors. Small, 2011, 7: 2454

    Google Scholar 

  24. Yuan C, Li J, Hou L, et al. Ultrathin mesoporous NiCo2O4 nanosheets supported on Ni foam as advanced electrodes for supercapacitors. Adv Funct Mater, 2012, 22: 4592–4597

    Article  Google Scholar 

  25. Jiao Y, Pei J, Chen D, et al. Mixed-metallic MOF based electrode materials for high performance hybrid supercapacitors. J Mater Chem A, 2017, 5: 1094–1102

    Article  Google Scholar 

  26. Zhang G, Wang T, Yu X, et al. Nanoforest of hierarchical Co3O4@NiCo2O4 nanowire arrays for high-performance supercapacitors. Nano Energy, 2013, 2: 586–594

    Article  Google Scholar 

  27. Zhou W, Liu X, Sang Y, et al. Enhanced performance of layered titanate nanowire-based supercapacitor electrodes by nickel ion exchange. ACS Appl Mater Interfaces, 2014, 6: 4578–4586

    Article  Google Scholar 

  28. Wei W, Mi L, Gao Y, et al. Partial ion-exchange of nickel-sulfidederived electrodes for high performance supercapacitors. Chem Mater, 2014, 26: 3418–3426

    Article  Google Scholar 

  29. Kong D, Cheng C, Wang Y, et al. Three-dimensional Co3O4@C@Ni3S2 sandwich-structured nanoneedle arrays: towards highperformance flexible all-solid-state asymmetric supercapacitors. J Mater Chem A, 2015, 3: 16150–16161

    Article  Google Scholar 

  30. Lin L, Liu J, Liu T, et al. Growth-controlled NiCo2S4 nanosheet arrays with self-decorated nanoneedles for high-performance pseudocapacitors. J Mater Chem A, 2015, 3: 17652–17658

    Article  Google Scholar 

  31. Zhang Q, Zhao B, Wang J, et al. High-performance hybrid supercapacitors based on self-supported 3D ultrathin porous quaternary Zn-Ni-Al-Co oxide nanosheets. Nano Energy, 2016, 28: 475–485

    Article  Google Scholar 

  32. Yang Y, Zhou M, Guo W, et al. NiCoO2 nanowires grown on carbon fiber paper for highly efficient water oxidation. Electrochim Acta, 2015, 174: 246–253

    Article  Google Scholar 

  33. Chen S, Yang G, Jia Y, et al. Three-dimensional NiCo2O4@NiWO4 core-shell nanowire arrays for high performance supercapacitors. J Mater Chem A, 2017, 5: 1028–1034

    Article  Google Scholar 

  34. Zhang L, Zhang D, Ren Z, et al. Mesoporous NiCo2O4 micro/nanospheres with hierarchical structures for supercapacitor and methanol electro-oxidation. ChemElectroChem, 2017, 4: 441–449

    Article  Google Scholar 

  35. Sun S, Wang S, Li S, et al. Asymmetric supercapacitors based on a NiCo2O4/three dimensional graphene composite and three dimensional graphene with high energy density. J Mater Chem A, 2016, 4: 18646–18653

    Article  Google Scholar 

  36. Chen R, Wang HY, Miao J, et al. A flexible high-performance oxygen evolution electrode with three-dimensional NiCo2O4 coreshell nanowires. Nano Energy, 2015, 11: 333–340

    Article  Google Scholar 

  37. Lu XF, Wu DJ, Li RZ, et al. Hierarchical NiCo2O4 nanosheets@ hollow microrod arrays for high-performance asymmetric supercapacitors. J Mater Chem A, 2014, 2: 4706–4713

    Article  Google Scholar 

  38. 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

    Article  Google Scholar 

  39. Zhou M, Lu F, Shen X, et al. One-pot construction of three dimensional CoMoO4/Co3O4 hybrid nanostructures and their application in supercapacitors. J Mater Chem A, 2015, 3: 21201–21210

    Article  Google Scholar 

  40. Zhong JH, Wang AL, Li GR, et al. Co3O4/Ni(OH)2 composite mesoporous nanosheet networks as a promising electrode for supercapacitor applications. J Mater Chem, 2012, 22: 5656–5665

    Article  Google Scholar 

  41. Gao Y, Mi L, Wei W, et al. Double metal ions synergistic effect in hierarchical multiple sulfide microflowers for enhanced supercapacitor performance. ACS Appl Mater Interfaces, 2015, 7: 4311–4319

    Article  Google Scholar 

  42. Yu L, Zhang G, Yuan C, et al. Hierarchical NiCo2O4@MnO2 coreshell heterostructured nanowire arrays on Ni foam as high-performance supercapacitor electrodes. Chem Commun, 2013, 49: 137–139

    Article  Google Scholar 

  43. Yu D, Wu B, Ge L, et al. Decorating nanoporous ZIF-67-derived NiCo2O4 shells on a Co3O4 nanowire array core for battery-type electrodes with enhanced energy storage performance. J Mater Chem A, 2016, 4: 10878–10884

    Article  Google Scholar 

  44. Zhang C, Geng X, Tang S, et al. NiCo2O4@rGO hybrid nanostructures on Ni foam as high-performance supercapacitor electrodes. J Mater Chem A, 2017, 5: 5912–5919

    Article  Google Scholar 

  45. Xiao J, Yang S. Bio-inspired synthesis of NaCl-type CoxNi1−x O (0 ≤ x < 1) nanorods on reduced graphene oxide sheets and screening for asymmetric electrochemical capacitors. J Mater Chem, 2012, 22: 12253–12262

    Article  Google Scholar 

  46. Qin T, Peng S, Hao J, et al. Flexible and wearable all-solid-state supercapacitors with ultrahigh energy density based on a carbon fiber fabric electrode. Adv Energ Mater, 2017, 6: 1700409

    Article  Google Scholar 

  47. Zhao Y, Hu L, Zhao S, et al. Preparation of MnCo2O4@Ni(OH)2 core-shell flowers for asymmetric supercapacitor materials with ultrahigh specific capacitance. Adv Funct Mater, 2016, 26: 4085–4093

    Article  Google Scholar 

  48. Yuan C, Li J, Hou L, et al. Polymer-assisted synthesis of a 3D hierarchical porous network-like spinel NiCo2O4 framework towards high-performance electrochemical capacitors. J Mater Chem A, 2013, 1: 11145–11151

    Article  Google Scholar 

  49. Wang R, Xia C, Wei N, et al. NiCo2O4@TiN core-shell electrodes through conformal atomic layer deposition for all-solid-state supercapacitors. Electrochim Acta, 2016, 196: 611–621

    Article  Google Scholar 

  50. Wang Z, Zhu Z, Qiu J, et al. High performance flexible solid-state asymmetric supercapacitors from MnO2/ZnO core-shell nanorods//specially reduced graphene oxide. J Mater Chem C, 2014, 2: 1331–1336

    Article  Google Scholar 

  51. Zhai T, Lu X, Ling Y, et al. A new benchmark capacitance for supercapacitor anodes by mixed-valence sulfur-doped V6O13−x . Adv Mater, 2014, 26: 5869–5875

    Article  Google Scholar 

  52. 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

    Article  Google Scholar 

  53. Liu J, Zhang L, Wu HB, et al. High-performance flexible asymmetric supercapacitors based on a new graphene foam/carbon nanotube hybrid film. Energ Environ Sci, 2014, 7: 3709–3719

    Article  Google Scholar 

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (61376011), the Gansu Provincial Natural Science Foundation of China (17JR5RA198) and the Fundamental Research Funds for the Central Universities (lzujbky-2017-k21).

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Authors and Affiliations

  1. Key Laboratory for Magnetism and Magnetic Materials of the Ministry of Education, School of Physical Science and Technology, Lanzhou University, Lanzhou, 730000, China

    Jiaxin Hao  (郝加新), Shanglong Peng  (彭尚龙), Tianfeng Qin  (秦天锋), Zilei Wang  (王子磊), Yuxiang Wen  (温昱祥), Deyan He  (贺德衍), Jiachi Zhang  (张加驰) & Zhiya Zhang  (张稚雅)

  2. College of Mathematics and Physics, Qingdao University of Science and technology, Qingdao, 266061, China

    Xiaoyan Fan  (范晓彦)

  3. Department of Materials Science and Engineering, University of Washington, Seattle, Washington, 98195-2120, USA

    Guozhong Cao  (曹国忠)

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  1. Jiaxin Hao  (郝加新)
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  2. Shanglong Peng  (彭尚龙)
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  3. Tianfeng Qin  (秦天锋)
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  5. Yuxiang Wen  (温昱祥)
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  6. Deyan He  (贺德衍)
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  7. Jiachi Zhang  (张加驰)
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  8. Zhiya Zhang  (张稚雅)
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  9. Xiaoyan Fan  (范晓彦)
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  10. Guozhong Cao  (曹国忠)
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Corresponding authors

Correspondence to Shanglong Peng  (彭尚龙) or Guozhong Cao  (曹国忠).

Additional information

Jiaxin Hao is a graduate student at Lanzhou University. His current research is focused on the design and optimization of electrode materials for energy storage.

Shanglong Peng received his BSc degree (2003) in Physics and PhD degree (2008) in Condensed Matter Physics from Lanzhou University. He is currently a professor at School of Physical Science and Technology, Lanzhou University. His current research is focused on the design of advanced electronic and energy materials, and control of surface and interface properties in energy related applications, mainly including solar cells and supercapacitor.

Guozhong Cao is a boeing-steiner professor of Materials Science and Engineering, Professor of Chemical Engineering, and Adjunct Professor of Mechanical Engineering at the University of Washington, Seattle, US. His current research is focused on chemical processing of nanomaterials for energy related applications including solar cells, rechargeable batteries, supercapacitors and hydrogen storage.

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Fabrication of hybrid Co3O4/NiCo2O4 nanosheets sandwiched by nanoneedles for high-performance supercapacitors using a novel electrochemical ion exchange

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Hao, J., Peng, S., Qin, T. et al. Fabrication of hybrid Co3O4/NiCo2O4 nanosheets sandwiched by nanoneedles for high-performance supercapacitors using a novel electrochemical ion exchange. Sci. China Mater. 60, 1168–1178 (2017). https://doi.org/10.1007/s40843-017-9139-8

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