Defect modulation of ZnMn2O4 nanotube arrays as high-rate and durable cathode for flexible quasi-solid-state zinc ion battery

https://doi.org/10.1016/j.cej.2021.129890Get rights and content

Highlights

  • A novel N-ZMO NTAs is developed as advanced cathode for ZIBs.

  • The N-ZMO NTAs have high electrical conductivity and stable architecture.

  • The flexible quasi-solid-state ZIBs show decent energy/power density with long-term stability.

Abstract

The exploration of a stable and high-rate cathode is very important for rechargeable Zn ion batteries (ZIBs). With unique merits of rich abundance, low price, and environmental friendliness, spinel ZnMn2O4 (ZMO) hold great promise as a cathode material for ZIBs. However, its inherent low electronic conductivity and large volume variation in the process of charge/discharge severely restrict the rate capability and durability. Herein, the novel N-doping coupled oxygen vacancies modulated ZMO nanotube arrays (NTAs) (N-ZMO NTAs) are fabricated as high-performance cathode for rechargeable ZIBs. Taking advantages of high electrical conductivity, fast ion diffusion, high surface area, sufficient active sites, and stable hollow nanotubular architecture, the N-ZMO NTAs show an admirable capacity (223 mA h g−1 at 0.1 A g−1), decent rate capability (133.3 mA h g−1 at 4 A g−1) and distinguished long-term durability (92.1% after 1500 cycles). Furthermore, a flexible quasi-solid-state ZIBs is fabricated with N-ZMO NTAs cathode, which achieves favorable energy density (214.6 W h kg−1), superb power density (4 kW kg−1), and impressive long-term stability (88.6% after 1500 cycles), outperforming most state-of-the-art ZIBs. This study may shed light on designing advanced cathodes for advanced ZIBs.

Introduction

With the booming of wearable, portable and implantable electronics, it is very urgent to exploit novel energy storage devices (ESDs) that have eminent energy and power densities, good cycling durability, high safety, and super flexibility.[1], [2], [3] Lithium-ion batteries (LIBs) have achieved great success in recent decades because of remarkable energy density and outstanding rechargeability. However, the high cost and shortage of lithium resources, toxic and flammable electrolytes, and unsatisfactory power density severely restrict its further development.[4], [5] As an alternative energy storage device, rechargeable Zn ion batteries (ZIBs) have recently attracted great interest of scientists due to the inherent advantages, such as good safety, abundant resources, cost-effective, environmental friendliness, large theoretical capacity, and low redox potential of Zn/Zn2+.[6], [7], [8] Up to the present, Prussian blue analogs[9] and MnO2 polymorphs[10] ZIBs have been exploited and made a good result. Unfortunately, compared with the large theoretical specific capacity (820 mAh g−1) of the zinc negative electrode, the reported capacity of positive electrode materials is still low, and the cycling stability also needs to be further improved.[11], [12], [13] To address this limitation, scientists have been committed to developing large-capacity cathode materials in past years.[14], [15], [16], [17], [18] So far, a wide range of materials have been designed as cathode materials for ZIBs and exhibit excellent electrochemical performance, such as molybdenum trioxide,[19], [20], [21] vanadium pentoxide,[22], [23], [24] metal vanadate,[25], [26], [27] vanadium disulfide,[28], [29] VNxOy,[30], [31] transition metal dichalcogenides,[32], [33], [34] and organic redox-active compounds[35], [36], [37], [38], [39]. In particular, Niu and his collaborators have successfully assembled a CaVO//Zn battery with CaVO cathode, which deliver a high capacity (300 mA h g−1 at 0.1 A g−1), superior rate capability (62 mA h g−1 at 30 A g−1) as well as admirable durability with almost no attenuation after 10 000 cycles.[40] Peng and coworkers employed oxygen-deficient vanadium oxide, which was prepared on the flexible carbon cloth as a robust cathode, and the assembled Od-VO//Zn device showed a high energy density of 298 Wh kg−1 with an ultralong lifespan.[41] Despite these considerable achievements, the great majority of cathode materials have so far been plagued by low capacity, poor rate performance, and short lifespan.[42] Yet, it is a challenging and urgent mission to develop novel cathode materials that have a large capacity, high-rate, and long cycling stability.

Spinel-structured oxides materials have shown great promise as desirable cathodes for ZIBs owing to their abundant oxidation states, enhanced redox couples, and reversible Zn2+ intercalation.[43], [44], [45], [46], [47], [48] To date, a variety of nanostructured spinel oxides materials, including Mn3O4,[43] LiMn2O4,[44], [47] ZnMn2O4 (ZMO),[45], [49] ZnCo2O4,[46] MgMn2O4,[48] have been explored and showed an impressive performance. Notably, ZMO with bivalent Zn at tetrahedral sites and trivalent Mn occupying octahedral sites has been extensively studied as a positive material for ZIBs given the large theoretical capacity, abundance, high redox potential, cost-effectiveness, and eco- friendliness. More importantly, ZMO exhibits enhanced redox couples and accessible active sites due to the unique diatomic synergistic effect.[50], [51] Recently, Chen Jun's group prepared a cation-deficient ZMO cathode nanomaterial and successfully assembled an aqueous ZMO/C//Zn device with 3 M Zn(CF3SO3)2 electrolyte, and this device could reach a decent specific capacity of 150 mA h g−1 at 50 mA g−1.[45] Based on a hollow porous ZMO cathode, the ZMO//Zn battery exhibited an appreciable specific capacity of 106.5 mA h g−1 when the current density was 100 mA g−1.[52] Despite these achievements, due to the intrinsically weak conductivity, insufficient active sites, and large volume change of ZMO, the rate performance and long-term durability of these current ZMO//Zn batteries are still not satisfactory. Exploring new ZMO based cathode materials with high intrinsic conductivity and structural stability is urgently desirable.

In this work, an effective and facile surface engineering strategy is demonstrated to ameliorate the intrinsic electronic structure of ZMO nanotube arrays (NTAs) (N-ZMO NTAs) using oxygen anion extraction and N modulation, which are supported on flexible carbon fiber cloth (CFC) as robust cathode for ZIBs. The NTAs support on interconnected CFC can endow with higher specific surface area, better permeability, faster electron, and ion transfer rate.[53], [54] Moreover, the stable hollow structure could efficaciously buffer the mechanical stress in the electrochemical process, thereby greatly enhance the cycle stability.[55] What is more, the introduced N­doping and oxygen vacancies could promote electron density, provide active sites, lower bandgap, and enhance Zn2+ diffusion kinetics, thus improving intrinsic electronic conductivity and surface capacitive contribution.[4], [56] As a consequence, the as-fabricated ZIBs based on the N-ZMO NTAs cathode delivers an admirable specific capacity (223 mA h g−1 at 0.1 A g−1), impressive rate capability (133.3 mA h g−1 at 4 A g−1) as well as desirable long-term durability (92.1% after 1500 cycles). Encouragingly, this flexible quasi-solid-state ZIBs also presented a satisfactory energy density (214.6 W h kg−1), large power density (4 kW kg−1) as well as ultralong cycle life with 88.6% capacity retention after 1500 cycle, outperforming most of the current ZIBs devices.

Section snippets

Experimental section

Synthesize of N-ZMO NTAs cathode: All chemical reagents were purchased from Aladdin with analytically pure (AR), which could be used directly without any purification treatment. Electrodeposition was conducted by galvanostatic electrolysis method in a typical two-electrode cell system, consisting of a graphite counter electrode and a commercial carbon cloth working electrode. The specific synthesis steps were as follows:

  • (1)

    ZnO nanorod arrays (NRAs) were prepared on the CFC by a simple

Results and discussion

Fig. 1a presents the fabrication procedures of N-ZMO NTAs. Firstly, the ZnO NRAs were uniformly grown over the surface of CFC (Figure S1a) by electrochemical deposition, and the vertically aligned ZnO NRAs have a 3 mm length and 300 nm diameter (Figure S1b). After that, the ZMO nanoparticles were deposited onto the surface of ZnO NRAs and form a core–shell structure, in which the ZnO NRAs were coated with ZMO nanoparticles (Figure S1c). Notably, the ZMO nanoparticles are perfectly coated onto

Conclusion

In summary, a novel high-performance N-ZMO NTAs cathode was fabricated for flexible quasi-solid-state ZIBs through an efficient defect engineering strategy. Benefiting from the N­doping coupled oxygen vacancies modulation, the N-ZMO NTAs cathode may be provided with good conductivity, efficient ion transport, rich active sites, and enhanced surface capacitive contribution. Furthermore, the 1D hollow NTAs nanoarchitecture can not only endow with a fast channel for zinc ion diffusion, but also

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

We acknowledge the Hainan Provincial Science and Technology Project (ZDYF2019160), Basic and Applied Basic Research Project of Guangdong Province (2019A1515110827), Science and Technology Planning Project of Guangzhou (201804010196, 2021), Education Commission of Guangdong Province (2019GKTSCX015), Advanced Functional Materials Scientific Research and Technical Service Team (X20190197) and Natural Science Project of Guangdong Industry Polytechnic (KJ2020-006).

References (79)

  • Y. Tao et al.

    Nickel and cobalt Co-substituted spinel ZnMn2O4@N-rGO for increased capacity and stability as a cathode material for rechargeable aqueous zinc-ion battery

    Electrochim. Acta

    (2020)
  • W. Li et al.

    A long-life aqueous Zn-ion battery based on Na3V2(PO4)2F3 cathode

    Energy Storage Mater.

    (2018)
  • J. Lee et al.

    Todorokite-type MnO2 as a zinc-ion intercalating material

    Electrochim. Acta

    (2013)
  • B. Lin et al.

    Birnessite Nanosheet Arrays with High K Content as a High-Capacity and Ultrastable Cathode for K-Ion Batteries

    Adv. Mater.

    (2019)
  • R. Zhang et al.

    Lithiophilic Sites in Doped Graphene Guide Uniform Lithium Nucleation for Dendrite-Free Lithium Metal Anodes

    Angew. Chem. Int. Ed.

    (2017)
  • Y. Zhang et al.

    Multiscale Graphene-Based Materials for Applications in Sodium Ion Batteries

    Adv. Energy Mater.

    (2019)
  • Y. Zeng 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)
  • P. Yu et al.

    Flexible Zn-ion batteries: recent progresses and challenges

    Small

    (2019)
  • Y. Zeng et al.

    Dendrite-Free Zinc Deposition Induced by Multifunctional CNT Frameworks for Stable Flexible Zn-Ion Batteries

    Adv. Mater.

    (2019)
  • M.H. Yu et al.

    A High-Rate Two-Dimensional Polyarylimide Covalent Organic Framework Anode for Aqueous Zn-Ion Energy Storage Devices

    J. Am. Chem. Soc.

    (2020)
  • C. Zhong et al.

    Decoupling electrolytes towards stable and high-energy rechargeable aqueous zinc–manganese dioxide batteries

    Nat. Energy

    (2020)
  • L. Zhang et al.

    Towards High-Voltage Aqueous Metal-Ion Batteries Beyond 1.5 V: The Zinc/Zinc Hexacyanoferrate System

    Adv. Energy Mater.

    (2015)
  • Y. Zhang et al.

    Defect Promoted Capacity and Durability of N-MnO2–x Branch Arrays via Low-Temperature NH3 Treatment for Advanced Aqueous Zinc Ion Batteries

    Small

    (2019)
  • C. Liu et al.

    Expanded hydrated vanadate for high-performance aqueous zinc-ion batteries

    Energy Environ. Sci.

    (2019)
  • X. Jia et al.

    Active Materials for Aqueous Zinc Ion Batteries: Synthesis, Crystal Structure, Morphology, and Electrochemistry

    Chem. Rev.

    (2020)
  • H. Geng et al.

    Electronic Structure Regulation of Layered Vanadium Oxide via Interlayer Doping Strategy toward Superior High-Rate and Low-Temperature Zinc-Ion Batteries

    Adv. Funct. Mater.

    (2020)
  • Y. Liu et al.

    Graphene Oxide Wrapped CuV2O6 Nanobelts as High-Capacity and Long-Life Cathode Materials of Aqueous Zinc-Ion Batteries

    ACS Nano

    (2019)
  • F. Wan et al.

    Reversible Oxygen Redox Chemistry in Aqueous Zinc-Ion Batteries

    Angew. Chem. Int. Ed.

    (2019)
  • P. He et al.

    Sodium Ion Stabilized Vanadium Oxide Nanowire Cathode for High-Performance Zinc-Ion Batteries

    Adv. Energy Mater.

    (2018)
  • F. Wan et al.

    Design Strategies for Vanadium-based Aqueous Zinc-Ion Batteries

    Angew. Chem. Int. Ed.

    (2019)
  • X. He et al.

    Stabilized Molybdenum Trioxide Nanowires as Novel Ultrahigh-Capacity Cathode for Rechargeable Zinc Ion Battery

    Adv. Sci.

    (2019)
  • Y. Liu et al.

    Interfacial Engineering Coupled Valence Tuning of MoO3 Cathode for High-Capacity and High-Rate Fiber-Shaped Zinc-Ion Batteries

    Small

    (2020)
  • T. Xiong et al.

    Hexagonal MoO3 as a zinc intercalation anode towards zinc metal-free zinc-ion batteries

    J. Mater. Chem. A

    (2020)
  • M. Yan et al.

    Water-Lubricated Intercalation in V2O5·nH2O for High-Capacity and High-Rate Aqueous Rechargeable Zinc Batteries

    Adv. Mater.

    (2018)
  • N. Zhang et al.

    Hydrated Layered Vanadium Oxide as a Highly Reversible Cathode for Rechargeable Aqueous Zinc Batteries

    Adv. Funct. Mater.

    (2019)
  • X. Wang et al.

    2D Amorphous V2O5/Graphene Heterostructures for High-Safety Aqueous Zn-Ion Batteries with Unprecedented Capacity and Ultrahigh Rate Capability

    Adv. Energy Mater.

    (2020)
  • C. Xia et al.

    Rechargeable Aqueous Zinc-Ion Battery Based on Porous Framework Zinc Pyrovanadate Intercalation Cathode

    Adv. Mater.

    (2018)
  • Q. Pang et al.

    H2V3O8 Nanowire/Graphene Electrodes for Aqueous Rechargeable Zinc Ion Batteries with High Rate Capability and Large Capacity

    Adv. Energy Mater.

    (2018)
  • P. Hu et al.

    Highly Durable Na2V6O16·1.63H2O Nanowire Cathode for Aqueous Zinc-Ion Battery

    Nano Lett.

    (2018)
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