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Oxygen vacancies-rich cobalt-doped NiMoO4 nanosheets for high energy density and stable aqueous Ni-Zn battery

富氧空位的钴掺杂NiMoO4纳米片用于高能量密 度和循环稳定性的水系镍锌电池

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Abstract

The enhancement of energy density and cycling stability is in urgent need for the widespread applications of aqueous rechargeable Ni-Zn batteries. Herein, a facile strategy has been employed to construct hierarchical Co-doped Ni-MoO4 nanosheets as the cathode for high-performance Ni-Zn battery. Benefiting from the merits of substantially improved electrical conductivity and increased concentration of oxygen vacancies, the NiMoO4 with 15% cobalt do** (denoted as CNMO-15) displays the best capacity of 361.4 mA h g−1 at a current density of 3 A g−1 and excellent cycle stability. Moreover, the assembled CNMO-15//Zn battery delivers a satisfactory specific capacity of 270.9 mA h g-1 at 2 A g−1 and a remarkable energy density of 474.1 W h kg−1 at 3.5 kW kg−1, together with a maximum power density of 10.3 kW kg−1 achieved at 118.8 W h kg−1. Noticeably, there is no capacity decay with a 119.8% retention observed after 5000 cycles, demonstrating its outstanding long lifespan. This work might provide valuable inspirations for the fabrication of high performance Ni Zn batteries with superior energy density and impressive stability.

摘要

提高能量密度和循环稳定性对推广水系可充电镍锌电池的 广泛应用至关重要. 我们采用一种简易的合成方法构建了Co掺杂 NiMoO4纳米片, 并将其作为**极材料用于高性能镍锌电池. 得益 于导电性和氧空位浓度的大幅度提升, 钴掺杂量为15%的电极材料 (CNMO-15)表现出突出的比容量及循环稳定性, 在3 A g−1的电流 密度下其容量高达361.4 mA h g−1. 此外, 以CNMO-15为**极组装 的镍锌电池(CNMO-15//Zn)也展现了优异的比容量(在2 A g−1的电 流密度下高达270.9 mA h g−1), 以及高能量密度(在3.5 kW kg−1的 功率密度下高达474.1 W h kg−1)和功率密度(在118.8 W h kg−1的能 量密度下高达10.3 kW kg−1). 值得注意的是, 该电池在循环5000圈 后容量没有损失, 保留了初始容量的119.8%, 表现出优异的循环稳 定性. 本研究可以为未来构建高能量密度和优异循环稳定性的镍 锌电池提供非常有价值的参考.

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References

  1. Huang J, Wang Z, Hou M, et al. Polyaniline-intercalated manganese dioxide nanolayers as a high-performance cathode material for an aqueous zinc-ion battery. Nat Commun, 2018, 9: 2906

    Google Scholar 

  2. Pan H, Shao Y, Yan P, et al. Reversible aqueous zinc/manganese oxide energy storage from conversion reactions. Nat Energy, 2016, 1: 16039

    CAS  Google Scholar 

  3. Simon P, Gogotsi Y, Dunn B. Where do batteries end and super-capacitors begin? Science, 2014, 343: 1210–1211

    CAS  Google Scholar 

  4. Li YJ, Cui L, Da PF, et al. Multiscale structural engineering of Ni-doped CoO nanosheets for zinc-air batteries with high power density. Adv Mater, 2018, 30: 1804653

    Google Scholar 

  5. He J, Chen Y, Manthiram A. Metal sulfide-decorated carbon sponge as a highly efficient electrocatalyst and absorbant for polysulfide in high-loading Li2S batteries. Adv Energy Mater, 2019, 9: 1900584

    Google Scholar 

  6. Naveed A, Yang H, Shao Y, et al. A highly reversible Zn anode with intrinsically safe organic electrolyte for long-cycle-life batteries. Adv Mater, 2019, 31: 1900668

    Google Scholar 

  7. Li X, Guan C, Hu Y, et al. Nanoflakes of Ni-Co LDH and Bi2O3 assembled in 3D carbon fiber network for high-performance aqueous rechargeable Ni/Bi battery. ACS Appl Mater Interfaces, 2017, 9: 26008–26015

    CAS  Google Scholar 

  8. Sarkar D, Shukla A, Sarma DD. Substrate integrated nickel-iron ultrabattery with extraordinarily enhanced performances. ACS Energy Lett, 2016, 1: 82–88

    CAS  Google Scholar 

  9. Lei D, Lee DC, Magasinski A, et al. Performance enhancement and side reactions in rechargeable nickel-iron batteries with nanostructured electrodes. ACS Appl Mater Interfaces, 2016, 8: 2088–2096

    CAS  Google Scholar 

  10. Zhao X, Ma L, Shen X. Co-based anode materials for alkaline rechargeable Ni/Co batteries: a review. J Mater Chem, 2012, 22: 277–285

    CAS  Google Scholar 

  11. Gao XP, Yao SM, Yan TY, et al. Alkaline rechargeable Ni/Co batteries: cobalt hydroxides as negative electrode materials. Energy Environ Sci, 2009, 2: 502–505

    CAS  Google Scholar 

  12. Zeng Y, Lin Z, Meng Y, et al. Flexible ultrafast aqueous rechargeable Ni//Bi battery based on highly durable single-crystalline bismuth nanostructured anode. Adv Mater, 2016, 28: 9188–9195

    CAS  Google Scholar 

  13. Hao Z, Xu L, Liu Q, et al. On-chip Ni-Zn microbattery based on hierarchical ordered porous Ni@Ni(OH)2 microelectrode with ultrafast ion and electron transport kinetics. Adv Funct Mater, 2019, 29: 1808470

    Google Scholar 

  14. Liu J, Guan C, Zhou C, et al. A flexible quasi-solid-state nickel-zinc battery with high energy and power densities based on 3D electrode design. Adv Mater, 2016, 28: 8732–8739

    CAS  Google Scholar 

  15. Meng L, Lin D, Wang J, et al. Electrochemically activated nickelcarbon composite as ultrastable cathodes for rechargeable nickel-zinc batteries. ACS Appl Mater Interfaces, 2019, 11: 14854–14861

    CAS  Google Scholar 

  16. Huang M, Li M, Niu C, et al. Recent advances in rational electrode designs for high-performance alkaline rechargeable batteries. Adv Funct Mater, 2019, 29: 1807847

    Google Scholar 

  17. Wang R, Han Y, Wang Z, et al. Nickel@nickel oxide core-shell electrode with significantly boosted reactivity for ultrahigh-energy and stable aqueous Ni-Zn battery. Adv Funct Mater, 2018, 28: 1802157

    Google Scholar 

  18. Lee DU, Fu J, Park MG, et al. Self-assembled NiO/Ni(OH)2 nanoflakes as active material for high-power and high-energy hybrid rechargeable battery. Nano Lett, 2016, 16: 1794–1802

    CAS  Google Scholar 

  19. Shang W, Yu W, Tan P, et al. Achieving high energy density and efficiency through integration: progress in hybrid zinc batteries. J Mater Chem A, 2019, 7: 15564–15574

    CAS  Google Scholar 

  20. Tan P, Chen B, Xu H, et al. Nanoporous NiO/Ni(OH)2 plates incorporated with carbon nanotubes as active materials of rechargeable hybrid zinc batteries for improved energy efficiency and high-rate capability. J Electrochem Soc, 2018, 165: A2119–A2126

    CAS  Google Scholar 

  21. Zeng Y, Lai Z, Han Y, et al. Oxygen-vacancy and surface modulation of ultrathin nickel cobaltite nanosheets as a high-energy cathode for advanced Zn-ion batteries. Adv Mater, 2018, 30: 1802396

    Google Scholar 

  22. Wang X, Li M, Wang Y, et al. A Zn-NiO rechargeable battery with long lifespan and high energy density. J Mater Chem A, 2015, 3: 8280–8283

    CAS  Google Scholar 

  23. Jian Y, Wang D, Huang M, et al. Facile synthesis of Ni(OH)2/carbon nanofiber composites for improving NiZn battery cycling life. ACS Sustain Chem Eng, 2017, 5: 6827–6834

    CAS  Google Scholar 

  24. Xu C, Liao J, Yang C, et al. An ultrafast, high capacity and superior longevity Ni/Zn battery constructed on nickel nanowire array film. Nano Energy, 2016, 30: 900–908

    CAS  Google Scholar 

  25. Gong M, Li Y, Zhang H, et al. Ultrafast high-capacity NiZn battery with NiAlCo-layered double hydroxide. Energy Environ Sci, 2014, 7: 2025–2032

    CAS  Google Scholar 

  26. Chen C, Yan D, Luo X, et al. Construction of core-shell Ni-MoO4@Ni-Co-S nanorods as advanced electrodes for high-performance asymmetric supercapacitors. ACS Appl Mater Interfaces, 2018, 20: 4662–4671

    Google Scholar 

  27. Qing C, Yang C, Chen M, et al. Design of oxygen-deficient NiMoO4 nanoflake and nanorod arrays with enhanced supercapacitive performance. Chem Eng J, 2018, 354: 182–190

    CAS  Google Scholar 

  28. Liu Z, Zhan C, Peng L, et al. A CoMoO4−Co2Mo3O8 hetero-structure with valence-rich molybdenum for a high-performance hydrogen evolution reaction in alkaline solution. J Mater Chem A, 2019, 7: 16761–16769

    CAS  Google Scholar 

  29. Zhang Z, Zhang H, Zhang X, et al. Facile synthesis of hierarchical CoMoO4@NiMoO4 core-shell nanosheet arrays on nickel foam as an advanced electrode for asymmetric supercapacitors. J Mater Chem A, 2016, 4: 18578–18584

    CAS  Google Scholar 

  30. Cheng D, Yang Y, **e J, et al. Hierarchical NiCo2O4@NiMoO4 core-shell hybrid nanowire/nanosheet arrays for high-performance pseudocapacitors. J Mater Chem A, 2015, 3: 14348–14357

    CAS  Google Scholar 

  31. Zhang P, Zhou J, Chen W, et al. Constructing highly-efficient electron transport channels in the 3D electrode materials for highrate supercapacitors: the case of NiCo2O4@NiMoO4 hierarchical nanostructures. Chem Eng J, 2017, 307: 687–695

    CAS  Google Scholar 

  32. Yang J, Liu W, Niu H, et al. Ultrahigh energy density battery-type asymmetric supercapacitors: NiMoO4 nanorod-decorated graphene and graphene/Fe2O3 quantum dots. Nano Res, 2018, 11: 4744–4758

    CAS  Google Scholar 

  33. Sharma GP, Pala RGS, Sivakumar S. Ultrasmall NiMoO4 robust nanoclusters-active carbon composite for high performance extrinsic pseudocapacitor. Electrochim Acta, 2019, 318: 607–616

    CAS  Google Scholar 

  34. Lei X, Ge S, Tan Y, et al. Bimetallic phosphosulfide Zn-Ni-P-S nanosheets as binder-free electrodes for aqueous asymmetric supercapacitors with impressive performance. J Mater Chem A, 2019, 7: 24908–24918

    CAS  Google Scholar 

  35. Huang J, Wei J, **ao Y, et al. When Al-doped cobalt sulfide nanosheets meet nickel nanotube arrays: a highly efficient and stable cathode for asymmetric supercapacitors. ACS Nano, 2018, 12: 3030–3041

    CAS  Google Scholar 

  36. Ling T, Zhang T, Ge B, et al. Well-dispersed nickel- and zinc-tailored electronic structure of a transition metal oxide for highly active alkaline hydrogen evolution reaction. Adv Mater, 2019, 31: 1807771

    Google Scholar 

  37. Wang R, Lu Y, Zhou L, et al. Oxygen-deficient tungsten oxide nanorods with high crystallinity: promising stable anode for asymmetric supercapacitors. Electrochim Acta, 2018, 283: 639–645

    CAS  Google Scholar 

  38. Chiu KL, Lin LY. Applied potential-dependent performance of the nickel cobalt oxysulfide nanotube/nickel molybdenum oxide nanosheet core-shell structure in energy storage and oxygen evolution. J Mater Chem A, 2019, 7: 4626–4639

    CAS  Google Scholar 

  39. Lin J, Yao L, Li Z, et al. Hybrid hollow spheres of carbon@ CoxNi1−xMoO4 as advanced electrodes for high-performance asymmetric supercapacitors. Nanoscale, 2019, 11: 3281–3291

    CAS  Google Scholar 

  40. Xu K, Ma S, Shen Y, et al. CuCo2O4 nanowire arrays wrapped in metal oxide nanosheets as hierarchical multicomponent electrodes for supercapacitors. Chem Eng J, 2019, 369: 363–369

    CAS  Google Scholar 

  41. Ruan Y, Lv L, Li Z, et al. Ni nanoparticles@Ni-Mo nitride nanorod arrays: a novel 3D-network hierarchical structure for high areal capacitance hybrid supercapacitors. Nanoscale, 2017, 9: 18032–18041

    CAS  Google Scholar 

  42. Lu Z, Wu X, Lei X, et al. Hierarchical nanoarray materials for advanced nickel-zinc batteries. Inorg Chem Front, 2015, 2: 184–187

    CAS  Google Scholar 

  43. Shi W, Mao J, Xu X, et al. An ultra-dense NiS2/reduced graphene oxide composite cathode for high-volumetric/gravimetric energy density nickel-zinc batteries. J Mater Chem A, 2019, 7: 15654–15661

    CAS  Google Scholar 

  44. Zhou L, Zhang X, Zheng D, et al. Ni3S2@PANI core-shell nanosheets as a durable and high-energy binder-free cathode for aqueous rechargeable nickel-zinc batteries. J Mater Chem A, 2019, 7: 10629–10635

    CAS  Google Scholar 

  45. Huang M, Xu Z, Hou C, et al. Intermediate phase α-β-Ni1−xCox-(OH)2/carbon nanofiber hybrid material for high-performance nickel-zinc battery. Electrochim Acta, 2019, 298: 127–133

    CAS  Google Scholar 

  46. Lu Y, Wang J, Zeng S, et al. An ultrathin defect-rich Co3O4 nanosheet cathode for high-energy and durable aqueous zinc ion batteries. J Mater Chem A, 2019, 7: 21678–21683

    CAS  Google Scholar 

  47. Zhang H, Liu Q, Wang J, et al. Boosting the Zn-ion storage capability of birnessite manganese oxide nanoflorets by La3+ intercalation. J Mater Chem A, 2019, 7: 22079–22083

    CAS  Google Scholar 

  48. Hu P, Wang T, Zhao J, et al. Ultrafast alkaline Ni/Zn battery based on Ni-foam-supported Ni3S2 nanosheets. ACS Appl Mater Interfaces, 2015, 7: 26396–26399

    CAS  Google Scholar 

  49. Zhang H, Zhang X, Li H, et al. Flexible rechargeable Ni//Zn battery based on self-supported NiCo2O4 nanosheets with high power density and good cycling stability. Green Energy Environ, 2018, 3: 56–62

    Google Scholar 

  50. Meng A, Yuan X, Shen T, et al. One-step synthesis of flower-like Bi2O3/Bi2Se3 nanoarchitectures and NiCoSe2/Ni0.85Se nanoparticles with appealing rate capability for the construction of high-energy and long-cycle-life asymmetric aqueous batteries. J Mater Chem A, 2019, 7: 17613–17625

    CAS  Google Scholar 

  51. Chao D, Zhu CR, Song M, 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

    Google Scholar 

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (51602049), the Fundamental Research Funds for the Central Universities (2232017D-15, GSIF-DH-M-2020002), and China Postdoctoral Science Foundation (2017M610217 and 2018T110322).

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Authors and Affiliations

  1. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai, 201620, China

    Yuenian Shen  (沈越年), Zhihao Li  (**志豪), Zhe Cui  (崔哲), Rujia Zou  (邹儒佳) & Kaibing Xu  (徐开兵)

  2. Research Center for Analysis and Measurement, Donghua University, Shanghai, 201620, China

    Kaibing Xu  (徐开兵)

  3. Department of Applied Physics, Donghua University, Shanghai, 201620, China

    Qian Liu  (刘倩)

  4. College of Mechanical and Automotive Engineering, Shanghai University of Engineering Science, Shanghai, 201620, China

    Ke Zhang  (张可) & Fang Yang  (杨方)

  5. College of Health Science and Environmental Engineering, Shenzhen Technology University, Shenzhen, 518118, China

    Junqing Hu  (胡俊青)

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  1. Yuenian Shen  (沈越年)
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Contributions

Shen Y and Zhang K performed the experiments and wrote the article. Liu Q, Li Z and Cui Z conducted the characterization and data analysis. Yang F, Zou R, Hu J and Xu K proposed the experimental design. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Qian Liu  (刘倩) or Kaibing Xu  (徐开兵).

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Conflict of interest

The authors declare no conflict of interest.

Yuenian Shen is currently a postgraduate student in the College of Materials Science and Engineering, Donghua University. His current interest focuses on the transition metal oxides for electrochemical energy storage and conversion applications.

Qian Liu is currently working at Donghua University. She received her BS degree in physics from Ludong University (2010) and her PhD in material science from Donghua University (2015). Her current research interests are focusing on 1D and 2D nanomaterials’ manipulation, transformations and atomic level understanding of electromechanical, energy conversion and energy storage systems.

Kaibing Xu received his PhD degree from Donghua University in 2015. Currently, he works in the Research Center for Analysis and Measurement at Donghua University. His research focuses on rational design and synthesis of nanocomposite materials for applications in electrochemical energy storage and conversion such as supercapacitors, alkaline rechargeable batteries and lithium ion batteries.

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Shen, Y., Zhang, K., Yang, F. et al. Oxygen vacancies-rich cobalt-doped NiMoO4 nanosheets for high energy density and stable aqueous Ni-Zn battery. Sci. China Mater. 63, 1205–1215 (2020). https://doi.org/10.1007/s40843-020-1292-6

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