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Inverse opal manganese dioxide constructed by few-layered ultrathin nanosheets as high-performance cathodes for aqueous zinc-ion batteries

Abstract

Considering the high safety, low-cost and high capacity, aqueous zinc ion batteries have been a potential candidate for energy storage ensuring smooth electricity supply. Herein, we have synthesized inverse opal manganese dioxide constructed by few-layered ultrathin nanosheets by a solution template method at mild temperature. The ultrathin nanosheets with the thickness as small as 1 nm are well separated without obvious aggregation. Used as cathode material for aqueous zinc ion batteries, the few-layered ultrathin nanosheets combined with the inverse opal structure guarantee excellent performance. A high specific discharge capacity of 262.9 mAh·g−1 is retained for the 100th cycle at a current density of 300 mA·g−1 with a high capacity retention of 95.6%. A high specific discharge capacity of 121 mAh·g−1 at a high current density of 2,000 mA·g−1 is achieved even after 5,000 long-term cycles. The ex-situ X-ray diffraction (XRD) patterns, selected-area electron diffraction (SAED) patterns and high-resolution transmission electron microscopy (HRTEM) results demonstrate that the discharge/charge processes involve the reversible formation of zinc sulfate hydroxide hydrate on the cathode while in-plane crystal structure of the layered birnessite MnO2 could be maintained. This unique structured MnO2 is a promising candidate as cathode material for high capacity, high rate capability and long-term aqueous zinc-ion batteries.

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References

  1. [1]

    Chu, S.; Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature 2012, 488, 294–303.

    Article  Google Scholar 

  2. [2]

    Braff, W. A.; Mueller, J. M.; Trancik, J. E. Value of storage technologies for wind and solar energy. Nat. Clim. Change 2016, 6, 964–969.

    Article  Google Scholar 

  3. [3]

    Barthelmie, R. J.; Pryor, S. C. Potential contribution of wind energy to climate change mitigation. Nat. Clim. Change 2014, 4, 684–688.

    Article  Google Scholar 

  4. [4]

    Ren, H.; Shao, H.; Zhang, L. J.; Guo, D.; Jin, Q.; Yu, R. B.; Wang, L.; Li, Y. L.; Wang, Y.; Zhao, H. J. et al. A new graphdiyne nanosheet/Pt nanoparticle-based counter electrode material with enhanced catalytic activity for dye-sensitized solar cells. Adv. Energy Mater. 2015, 5, 1500296.

    Article  Google Scholar 

  5. [5]

    Mizushima, K.; Jones, P. C.; Wiseman, P. J.; Goodenough, J. B. LixCoO2 (0< x ≤ −1): A new cathode material for batteries of high energy density. Mater. Res. Bull. 1980, 15, 783–789.

    Article  Google Scholar 

  6. [6]

    Liu, T.; Zhang, M.; Wang, Y. L.; Wang, Q. Y.; Lv, C.; Liu, K. X.; Suresh, S.; Yin, Y. H.; Hu, Y. Y.; Li, Y. S. et al. Engineering the surface/interface of horizontally oriented carbon nanotube macrofilm for foldable lithium-ion battery withstanding variable weather. Adv. Energy Mater. 2018, 8, 1802349.

    Article  Google Scholar 

  7. [7]

    Yang, H.; Qi, K.; Gong, L. Q.; Liu, W. L.; Zaman, S.; Guo, X. P.; Qiu, Y. B.; Xia, B. Y. Lead oxide enveloped in N-doped graphene oxide composites for enhanced high-rate partial-state-of-charge performance of lead-acid battery. ACS Sustain. Chem. Eng. 2018, 6, 11408–11413.

    Article  Google Scholar 

  8. [8]

    Wang, D. X.; Chen, N.; Li, M. L.; Wang, C. Z.; Ehrenberg, H.; Bie, X. F.; Wei, Y. J.; Chen, G.; Du, F. Na3V2(PO4)3/C composite as the intercalationtype anode material for sodium-ion batteries with superior rate capability and long-cycle life. J. Mater. Chem. A 2015, 3, 8636–8642.

    Article  Google Scholar 

  9. [9]

    Huang, Z. D.; Hou, H. S.; Zhang, Y.; Wang, C.; Qiu, X. Q.; Ji, X. B. Layer-tunable phosphorene modulated by the cation insertion rate as a sodium-storage anode. Adv. Mater. 2017, 29, 1702372.

    Article  Google Scholar 

  10. [10]

    Ge, P.; Hou, H. S.; Banks, C. E.; Foster, C. W.; Li, S. J.; Zhang, Y.; He, J. Y.; Zhang, C. Y.; Ji, X. B. Binding MoSe2 with carbon constrained in carbonous nanosphere towards high-capacity and ultrafast Li/Na-ion storage. Energy Stor. Mater. 2018, 12, 310–323.

    Article  Google Scholar 

  11. [11]

    Li, M.; Lu, J.; Chen, Z. W.; Amine, K. 30Years of lithium-ion batteries. Adv. Mater. 2018, 30, 1800561.

    Article  Google Scholar 

  12. [12]

    Ren, H.; Yu, R. B.; Wang, J. Y.; Jin, Q.; Yang, M.; Mao, D.; Kisailus, D.; Zhao, H. J.; Wang, D. Multishelled TiO2 hollow microspheres as anodes with superior reversible capacity for lithium ion batteries. Nano Lett. 2014, 14, 6679–6684.

    Article  Google Scholar 

  13. [13]

    Ren, H.; Sun, J. J.; Yu, R. B.; Yang, M.; Gu, L.; Liu, P. R.; Zhao, H. J.; Kisailus, D.; Wang, D. Controllable synthesis of mesostructures from TiO2 hollow to porous nanospheres with superior rate performance for lithium ion batteries. Chem. Sci. 2016, 7, 793–798.

    Article  Google Scholar 

  14. [14]

    Wang, F.; Suo, L. M.; Liang, Y. J.; Yang, C. Y.; Han, F. D.; Gao, T.; Sun, W.; Wang, C. S. Spinel LiNi0.5Mn1.5O4 Cathode for high-energy aqueous lithium-ion batteries. Adv. Energy Mater. 2017, 7, 1600922.

    Article  Google Scholar 

  15. [15]

    Wang, H. B.; Zhang, T. R.; Chen, C.; Ling, M.; Lin, Z.; Zhang, S. Q.; Pan, F.; Liang, C. D. High-performance aqueous symmetric sodium-ion battery using NASICON-structured Na2VTi(PO4)3. Nano Res. 2018, 11, 490–498.

    Article  Google Scholar 

  16. [16]

    Wang, Y. G.; Yi, J.; Xia, Y. Y. Recent progress in aqueous lithium-ion batteries. Adv. Energy Mater. 2012, 2, 830–840.

    Article  Google Scholar 

  17. [17]

    Luo, J. Y.; Cui, W. J.; He, P.; Xia, Y. Y. Raising the cycling stability of aqueous lithium-ion batteries by eliminating oxygen in the electrolyte. Nat. Chem. 2010, 2, 760–765.

    Article  Google Scholar 

  18. [18]

    Li, Z.; Young, D.; Xiang, K.; Carter, W. C.; Chiang, Y. M. Towards high power high energy aqueous sodium-ion batteries: The NaTi2(PO4)3/Na0.44MnO2 system. Adv. Energy Mater. 2013, 3, 290–294.

    Article  Google Scholar 

  19. [19]

    Wessells, C. D.; Peddada, S. V.; Huggins, R. A.; Cui, Y. Nickel hexacyanoferrate nanoparticle electrodes for aqueous sodium and potassium ion batteries. Nano Lett. 2011, 11, 5421–5425.

    Article  Google Scholar 

  20. [20]

    Guduru, R. K.; Icaza, J. C. A brief review on multivalent intercalation batteries with aqueous electrolytes. Nanomaterials 2016, 6, 41.

    Article  Google Scholar 

  21. [21]

    Chen, L.; Bao, J. L.; Dong, X.; Truhlar, D. G.; Wang, Y.; Wang, C.; Xia, Y. Aqueous Mg-ion battery based on polyimide anode and prussian blue cathode. ACS Energy Lett. 2017, 2, 1115–1121.

    Article  Google Scholar 

  22. [22]

    Verma, V.; Kumar, S.; Manalastas, W. Jr.; Satish, R.; Srinivasan, M. Progress in rechargeable aqueous zinc-and aluminum-ion battery electrodes: Challenges and outlook. Adv. Sustain. Syst. 2019, 3, 1800111.

    Article  Google Scholar 

  23. [23]

    Alfaruqi, M. H.; Mathew, V.; Song, J. J.; Kim, S.; Islam, S.; Pham, D. T.; Jo, J.; Kim, S.; Baboo, J. P.; Xiu, Z. L. et al. Electrochemical zinc intercalation in lithium vanadium oxide: A high-capacity zinc-ion battery cathode. Chem. Mater. 2017, 29, 1684–1694.

    Article  Google Scholar 

  24. [24]

    Yan, M. Y.; He, P.; Chen, Y.; Wang, S. Y.; Wei, Q. L.; Zhao, K. N.; Xu, X.; An, Q. Y.; Shuang, Y.; Shao, Y. Y. et al. Water-lubricated intercalation in V2O5·nH2O for high-capacity and high-rate aqueous rechargeable zinc batteries. Adv. Mater. 2018, 30, 1703725.

    Article  Google Scholar 

  25. [25]

    Kundu, D.; Adams, B. D.; Duffort, V.; Vajargah, S. H.; Nazar, L. F. A high-capacity and long-life aqueous rechargeable zinc battery using a metal oxide intercalation cathode. Nat. Energy 2016, 1, 16119.

    Article  Google Scholar 

  26. [26]

    Hu, P.; Zhu, T.; Wang, X. P.; Wei, X. J.; Yan, M. Y.; Li, J. T.; Luo, W.; Yang, W.; Zhang, W. C.; Zhou, L. et al. Highly durable Na2V6O16·1.63H2O nanowire cathode for aqueous zinc-ion battery. Nano Lett. 2018, 18, 1758–1763.

    Article  Google Scholar 

  27. [27]

    Wei, T. Y.; Li, Q.; Yang, G. Z.; Wang, C. X. High-rate and durable aqueous zinc ion battery using dendritic V10O24·12H2O cathode material with large interlamellar spacing. Electrochim. Acta 2018, 287, 60–67.

    Article  Google Scholar 

  28. [28]

    Xia, C.; Guo, J.; Li, P.; Zhang, X. X.; Alshareef, H. N. Highly stable aqueous zinc-ion storage using a layered calcium vanadium oxide bronze cathode. Angew. Chem., Int. Ed. 2018, 57, 3943–3948.

    Article  Google Scholar 

  29. [29]

    Zhang, L. Y.; Chen, L.; Zhou, X. F.; Liu, Z. P. Towards high-voltage aqueous metal-ion batteries beyond 1.5 V: The zinc/zinc hexacyanoferrate system. Adv. Energy Mater. 2015, 5, 1400930.

    Article  Google Scholar 

  30. [30]

    Trócoli, R.; La Mantia, F. An aqueous zinc-ion battery based on copper hexacyanoferrate. ChemSusChem. 2015, 8, 481–485.

    Article  Google Scholar 

  31. [31]

    Zhang, N.; Cheng, F. Y.; Liu, Y. C.; Zhao, Q.; Lei, K. X.; Chen, C. C.; Liu, X. S.; Chen, J. Cation-deficient spinel ZnMn2O4 cathode in Zn(CF3SO3)2 electrolyte for rechargeable aqueous Zn-ion battery. J. Am. Chem. Soc. 2016, 138, 12894–12901.

    Article  Google Scholar 

  32. [32]

    Zhu, C. Y.; Fang, G. Z.; Zhou, J.; Guo, J. H.; Wang, Z. Q.; Wang, C.; Li, J. Y.; Tang, Y.; Liang, S. Q. Binder-free stainless steel@Mn3O4 nanoflower composite: A high-activity aqueous zinc-ion battery cathode with highcapacity and long-cycle-life. J. Mater. Chem. A 2018, 6, 9677–9683.

    Article  Google Scholar 

  33. [33]

    Pan, H. L.; Shao, Y. Y.; Yan, P. F.; Cheng, Y. W.; Han, K. S.; Nie, Z. M.; Wang, C. M.; Yang, J. H.; Li, X. L.; Bhattacharya, P. et al. Reversible aqueous zinc/manganese oxide energy storage from conversion reactions. Nat. Energy 2016, 1, 16039.

    Article  Google Scholar 

  34. [34]

    Sun, W.; Wang, F.; Hou, S.; Yang, C. Y.; Fan, X. L.; Ma, Z. H.; Gao, T.; Han, F. D.; Hu, R. Z.; Zhu, M. et al. Zn/MnO2 battery chemistry with H+ and Zn2+ coinsertion. J. Am. Chem. Soc. 2017, 139, 9775–9778.

    Article  Google Scholar 

  35. [35]

    Xu, C. J.; Li, B. H.; Du, H. D.; Kang, F. Y. Energetic zinc ion chemistry: The rechargeable zinc ion battery. Angew. Chem. 2012, 124, 957–959.

    Article  Google Scholar 

  36. [36]

    Zhang, N.; Cheng, F. Y.; Liu, J. X.; Wang, L. B.; Long, X. H.; Liu, X. S.; Li, F. J.; Chen, J. Rechargeable aqueous zinc-manganese dioxide batteries with high energy and power densities. Nat. Commun. 2017, 8, 405.

    Article  Google Scholar 

  37. [37]

    Lee, B.; Lee, H. R.; Kim, H.; Chung, K. Y.; Cho, B. W.; Oh, S. H. Elucidating the intercalation mechanism of zinc ions into α-MnO2 for rechargeable zinc batteries. Chem. Commun. 2015, 51, 9265–9268.

    Article  Google Scholar 

  38. [38]

    Alfaruqi, M. H.; Mathew, V.; Gim, J.; Kim, S.; Song, J. J.; Baboo, J. P.; Choi, S. H.; Kim, J. Electrochemically induced structural transformation in a γ-MnO2 cathode of a high capacity zinc-ion battery system. Chem. Mater. 2015, 27, 3609–3620.

    Article  Google Scholar 

  39. [39]

    Huang, J. H.; Wang, Z.; Hou, M. Y.; Dong, X. L.; Liu, Y.; Wang, Y. G.; Xia, Y. Y. Polyaniline-intercalated manganese dioxide nanolayers as a highperformance cathode material for an aqueous zinc-ion battery. Nat. Commun. 2018, 9, 2906.

    Article  Google Scholar 

  40. [40]

    Alfaruqi, M. H.; Gim, J.; Kim, S.; Song, J. J.; Pham, D. T.; Jo, J.; Xiu, Z. L.; Mathew, V.; Kim, J. A layered δ-MnO2 nanoflake cathode with high zinc-storage capacities for eco-friendly battery applications. Electrochem. Commun. 2015, 60, 121–125.

    Article  Google Scholar 

  41. [41]

    Liu, Z. N.; Xu, K. L.; Sun, H.; Yin, S. Y. One-step synthesis of single-layer MnO2 nanosheets with multi-role sodium dodecyl sulfate for high-performance pseudocapacitors. Small 2015, 11, 2182–2191.

    Article  Google Scholar 

  42. [42]

    Mendoza-Sánchez, B.; Coelho, J.; Pokle, A.; Nicolosi, V. A 2D graphenemanganese oxide nanosheet hybrid synthesized by a single step liquid-phase co-exfoliation method for supercapacitor applications. Electrochim. Acta 2015, 174, 696–705.

    Article  Google Scholar 

  43. [43]

    Sun, Y. G.; Wang, L.; Liu, Y. Z.; Ren, Y. Birnessite-type MnO2 nanosheets with layered structures under high pressure: Elimination of crystalline stacking faults and oriented laminar assembly. Small 2015, 11, 300–305.

    Article  Google Scholar 

  44. [44]

    Thanh, N. T. K.; Maclean, N.; Mahiddine, S. Mechanisms of nucleation and growth of nanoparticles in solution. Chem. Rev. 2014, 114, 7610–7630.

    Article  Google Scholar 

  45. [45]

    Qu, J. Y.; Shi, L.; He, C. X.; Gao, F.; Li, B. B.; Zhou, Q.; Hu, H.; Shao, G. H.; Wang, X. Z.; Qiu, J. S. Highly efficient synthesis of graphene/MnO2 hybrids and their application for ultrafast oxidative decomposition of methylene blue. Carbon 2014, 66, 485–492.

    Article  Google Scholar 

  46. [46]

    Zhu, C. Z.; Guo, S. J.; Fang, Y. X.; Han, L.; Wang, E. K.; Dong, S. J. One-step electrochemical approach to the synthesis of Graphene/MnO2 nanowall hybrids. Nano Res. 2011, 4, 648–657.

    Article  Google Scholar 

  47. [47]

    Nesbitt, H. W.; Banerjee, D. Interpretation of XPS Mn(2p) spectra of Mn oxyhydroxides and constraints on the mechanism of MnO2 precipitation. Am. Mineral. 1998, 83, 305–315.

    Article  Google Scholar 

  48. [48]

    Biesinger, M. C.; Payne, B. P.; Grosvenor, A. P.; Lau, L. W. M.; Gerson, A. R.; Smart, R. S. C. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni. Appl. Surf. Sci. 2011, 257, 2717–2730.

    Article  Google Scholar 

  49. [49]

    Banerjee, D.; Nesbitt, H. W. XPS study of dissolution of birnessite by humate with constraints on reaction mechanism. Geochim. Cosmochim. Acta 2001, 65, 1703–1714.

    Article  Google Scholar 

  50. [50]

    Lian, P. C.; Dong, Y. F.; Wu, Z. S.; Zheng, S. H.; Wang, X. H.; Wang, S.; Sun, C. L.; Qin, J. Q.; Shi, X. Y.; Bao, X. H. Alkalized Ti3C2 MXene nanoribbons with expanded interlayer spacing for high-capacity sodium and potassium ion batteries. Nano Energy 2017, 40, 1–8.

    Article  Google Scholar 

  51. [51]

    Chen, X.; Yan, S. J.; Wang, N.; Peng, S. K.; Wang, C.; Hong, Q. H.; Zhang, X. Y.; Dai, S. L. Facile synthesis and characterization of ultrathin δ-MnO2 nanoflakes. RSC Adv. 2017, 7, 55734–55740.

    Article  Google Scholar 

  52. [52]

    Dang, L. Y.; Wei, C. Z.; Ma, H. F.; Lu, Q. Y.; Gao, F. Three-dimensional honeycomb-like networks of birnessite manganese oxide assembled by ultrathin two-dimensional nanosheets with enhanced Li-ion battery performances. Nanoscale 2015, 7, 8101–8109.

    Article  Google Scholar 

  53. [53]

    Wang, J.; Polleux, J.; Lim, J.; Dunn, B. Pseudocapacitive contributions to electrochemical energy storage in TiO2 (anatase) nanoparticles. J. Phys. Chem. C 2007, 111, 14925–14931.

    Article  Google Scholar 

  54. [54]

    Muller, G. A.; Cook, J. B.; Kim, H. S.; Tolbert, S. H.; Dunn, B. High performance pseudocapacitor based on 2D layered metal chalcogenide nanocrystals. Nano Lett. 2015, 15, 1911–1917.

    Article  Google Scholar 

  55. [55]

    Chao, D. L.; Zhu, C. R.; Song, M.; Liang, P.; Zhang, X.; Tiep, N. H.; Zhao, H. F.; Wang, J.; Wang, R. M.; Zhang, H. et al. A high-rate and stable quasi-solid-state zinc-ion battery with novel 2D layered zinc orthovanadate array. Adv. Mater. 2018, 30, 1803181.

    Article  Google Scholar 

  56. [56]

    Nakayama, N.; Ohmoto, K.; Fujiwara, K.; Nakatsuka, A. A TEM study of birnessite-type K0.33MnO2-in-plane ordering and layer stacking. Trans. Mater. Res. Soc. Jpn. 2010, 35, 381–384.

    Article  Google Scholar 

  57. [57]

    Li, H. F.; Han, C. P.; Huang, Y.; Huang, Y.; Zhu, M. S.; Pei, Z. X.; Xue, Q.; Wang, Z. F.; Liu, Z. X.; Tang, Z. J. et al. An extremely safe and wearable solid-state zinc ion battery based on a hierarchical structured polymer electrolyte. Energy Environ. Sci. 2018, 11, 941–951.

    Article  Google Scholar 

  58. [58]

    Ma, L. T.; Chen, S. M.; Pei, Z. X.; Li, H. F.; Wang, Z. F.; Liu, Z. X.; Tang, Z. J.; Zapien, J. A.; Zhi, C. Y. Flexible waterproof rechargeable hybrid zinc batteries initiated by multifunctional oxygen vacancies-rich cobalt oxide. ACS Nano 2018, 12, 8597–8605.

    Article  Google Scholar 

  59. [59]

    Ma, L. T.; Chen, S. M.; Li, H. F.; Ruan, Z. H.; Tang, Z. J.; Liu, Z. X.; Wang, Z. F.; Huang, Y.; Pei, Z. X.; Zapien, J. A. et al. Initiating a mild aqueous electrolyte Co3O4/Zn battery with 2.2 V-high voltage and 5000-cycle lifespan by a Co(III) rich-electrode. Energy Environ. Sci. 2018, 11, 2521–2530.

    Article  Google Scholar 

  60. [60]

    Hoang, T. K. A.; Doan, T. N. L.; Sun, K. E. K.; Chen, P. Corrosion chemistry and protection of zinc & zinc alloys by polymer-containing materials for potential use in rechargeable aqueous batteries. RSC Adv. 2015, 5, 41677–41691.

    Article  Google Scholar 

  61. [61]

    Kundu, D.; Hosseini Vajargah, S.; Wan, L. W.; Adams, B.; Prendergast, D.; Nazar, L. F. Aqueous vs. nonaqueous Zn-ion batteries: Consequences of the desolvation penalty at the interface. Energy Environ. Sci. 2018, 11, 881–892.

    Article  Google Scholar 

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Acknowledgements

The work was financially supported by the National Research Foundation of Singapore (NRF) Investigatorship, award Number NRF2016NRF-NRFI001-22. The authors also acknowledge the Facility for Analysis, Characterization, Testing and Simulation (FACTS), Nanyang Technological University, Singapore, for use of the TEM JEOL 2010UHR, JEOL 2100F, FESEM JEOL 7600F, XPS Kratos AXIS Supra and XRD Bruker D8 Advance facilities.

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Correspondence to Srinivasan Madhavi or Qingyu Yan.

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Inverse opal manganese dioxide constructed by few-layered ultrathin nanosheets as high-performance cathodes for aqueous zinc-ion batteries

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Ren, H., Zhao, J., Yang, L. et al. Inverse opal manganese dioxide constructed by few-layered ultrathin nanosheets as high-performance cathodes for aqueous zinc-ion batteries. Nano Res. 12, 1347–1353 (2019). https://doi.org/10.1007/s12274-019-2303-1

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Keywords

  • inverse opal
  • ultrathin
  • few-layered nanosheets
  • MnO2
  • zinc ion batteries