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Research Article

Coupling N-doping and rich oxygen vacancies in mesoporous ZnMn2O4 nanocages toward advanced aqueous zinc ion batteries

Can Huang1, Qiufan Wang1(), Daohong Zhang1(), Guozhen Shen2()
Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education & Hubei Key Laboratory of Catalysis and Materials Science, Hubei R&D Center of Hyperbranched Polymers Synthesis and Applications, School of Chemistry and Materials Science, South-Central Minzu University, Wuhan 430074, China
School of Integrated Circuits and Electronics, Beijing Institute of Technology, Beijing 100081, China
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A mesoporous ZnMn2O4 (ZMO) nanocage coupled with nitrogen doping and oxygen vacancies is prepared by defect engineering and rational structural design as a high-performance cathode material for rechargeable zinc-ion (Zn2+) batteries (ZIBs). The cathode material exhibits excellent ability of Zn2+ storage, good rate, and stable cycling performance.

Abstract

The development of a high specific capacity and stable manganese (Mn)-based cathode material is very attractive for aqueous zinc-ion (Zn2+) batteries (ZIBs). However, the inherent low electrical conductivity and volume expansion challenges limit its stability improvement. Here, a mesoporous ZnMn2O4 (ZMO) nanocage (N-ZMO) coupled with nitrogen doping and oxygen vacancies is prepared by defect engineering and rational structural design as a high-performance cathode material for rechargeable ZIBs. The oxygen vacancies enhance the electrical conductivity of the material and the nitrogen doping releases the strong electrostatic force of the material to maintain a higher structural stability. Interestingly, N-ZMO exhibits excellent ability of Zn2+ storage (225.4 mAh·g−1 at 0.3 A·g−1), good rate, and stable cycling performance (88.4 mAh·g−1 after 1,000 cycles at 3 A·g−1). Furthermore, a flexible quasi-solid-state device with high energy density (261.6 Wh·kg−1) is assembled, demonstrating long-lasting durability. We believe that the strategy in this study can provide a new approach for developing aqueous ZIBs.

Keywords

nitrogen (N)-dopingoxygen vacanciesdefectzinc-ion (Zn2+) storage flexible quasi-solid-state device

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References

1

Li, C. P.; Xie, X. S.; Liang, S. Q.; Zhou, J. Issues and future perspective on zinc metal anode for rechargeable aqueous zinc-ion batteries. Energy Environ. Mater. 2020, 3, 146–159.

Crossref Google Scholar
2

Cao, F. Q.; Wu, B. H.; Li, T. Y.; Sun, S. T.; Jiao, Y. C.; Wu, P. Y. Mechanoadaptive morphing gel electrolyte enables flexible and fast-charging Zn-ion batteries with outstanding dendrite suppression performance. Nano Res. 2022, 15, 2030–2039.

Crossref Google Scholar
3
Yang, X. Z.; Li, W. P.; Lv, J. Z.; Sun, G. J.; Shi, Z. X.; Su, Y. W.; Lian, X. Y.; Shao, Y. Y.; Zhi, A. M.; Tian, X. Z. et al. In situ separator modification via CVD-derived N-doped carbon for highly reversible Zn metal anodes. Nano Res., in press, https://doi.org/10.1007/s12274-021-3957-z.
Crossref
4

Li, W. J.; Gao, X.; Chen, Z. Y.; Guo, R. T.; Zou, G. Q.; Hou, H. S.; Deng, W. T.; Ji, X. B.; Zhao, J. Electrochemically activated MnO cathodes for high performance aqueous zinc-ion battery. Chem. Eng. J. 2020, 402, 125509.

Crossref Google Scholar
5

Fu, Y. Q.; Wei, Q. L.; Zhang, G. X.; Wang, X. M.; Zhang, J. H.; Hu, Y. F.; Wang, D. N.; Zuin, L.; Zhou, T.; Wu, Y. C. et al. High-performance reversible aqueous Zn-ion battery based on porous MnOx nanorods coated by MOF-derived N-doped carbon. Adv. Energy Mater. 2018, 8, 1801445.

Crossref Google Scholar
6

Tan, Q. Y.; Li, X. T.; Zhang, B.; Chen, X.; Tian, Y. W.; Wan, H. Z.; Zhang, L. S.; Miao, L.; Wang, C.; Gan, Y. et al. Valence engineering via in situ carbon reduction on octahedron sites Mn3O4 for ultra-long cycle life aqueous Zn-ion battery. Adv. Energy Mater. 2020, 10, 2001050.

Crossref Google Scholar
7

Zhu, H. W.; Ge, J.; Peng, Y. C.; Zhao, H. Y.; Shi, L. A.; Yu, S. H. Dip-coating processed sponge-based electrodes for stretchable Zn-MnO2 batteries. Nano Res. 2018, 11, 1554–1562.

Crossref Google Scholar
8

Sun, Q. H.; He, J. J.; Li, X. D.; Lu, T. T.; Si, W. Y.; Zhao, F. H.; Wang, K.; Huang, C. S. In-situ synthesis of graphdiyne on Mn3O4 nanoparticles for efficient Zn ions diffusion and storage. Chem. Eng. J. 2022, 432, 134402.

Crossref Google Scholar
9

Lee, G. J.; Abbas, M. A.; Lee, M. D.; Lee, J.; Lee, J.; Bang, J. H. Lithiation mechanism change driven by thermally induced grain fining and its impact on the performance of LiMn2O4 in lithium-ion batteries. Small 2020, 16, 2002292.

Crossref Google Scholar
10

Yu, H.; Fan, H. S.; Yadian, B.; Tan, H. T.; Liu, W. L.; Hng, H. H.; Huang, Y. Z.; Yan, Q. Y. General approach for MOF-derived porous spinel AFe2O4 hollow structures and their superior lithium storage properties. ACS Appl. Mater. Interfaces 2015, 7, 26751–26757.

Crossref Google Scholar
11

Cai, W. L.; Song, Y. Z.; Fang, Y. T.; Wang, W. W.; Yu, S. L.; Ao, H. S.; Zhu, Y. C.; Qian, Y. T. Defect engineering on carbon black for accelerated Li-S chemistry. Nano Res. 2020, 13, 3315–3320.

Crossref Google Scholar
12

Li, Q. L.; Zhang, Q. C.; Zhou, Z. Y.; Gong, W. B.; Liu, C. L.; Feng, Y. B.; Hong, G.; Yao, Y. G. Boosting Zn-ion storage capability of self-standing Zn-doped Co3O4 nanowire array as advanced cathodes for high-performance wearable aqueous rechargeable Co//Zn batteries. Nano Res. 2021, 14, 91–99.

Crossref Google Scholar
13

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.

Crossref Google Scholar
14

Zhang, H. Z.; Wang, J.; Liu, Q. Y.; He, W. Y.; Lai, Z. Z.; Zhang, X. Y.; Yu, M. H.; Tong, Y. X.; Lu, X. H. Extracting oxygen anions from ZnMn2O4: Robust cathode for flexible all-solid-state Zn-ion batteries. Energy Storage Mater. 2019, 21, 154–161.

Crossref Google Scholar
15

Qiu, W. D.; Xiao, H. B.; Feng, H. J.; Lin, Z. C.; Gao, H.; He, W. T.; Lu, X. H. Defect modulation of ZnMn2O4 nanotube arrays as high-rate and durable cathode for flexible quasi-solid-state zinc ion battery. Chem. Eng. J. 2021, 422, 129890.

Crossref Google Scholar
16

Zhang, J.; Luan, Y. P.; Lyu, Z. Y.; Wang, L. J.; Xu, L. L.; Yuan, K. D.; Pan, F.; Lai, M.; Liu, Z. L.; Chen, W. Synthesis of hierarchical porous δ-MnO2 nanoboxes as an efficient catalyst for rechargeable Li-O2 batteries. Nanoscale 2015, 7, 14881–14888.

Crossref Google Scholar
17

Zeng, Y. X.; Wang, Y.; Jin, Q.; Pei, Z. H.; Luan, D. Y.; Zhang, X. T.; Lou, X. W. Rationally designed Mn2O3–ZnMn2O4 hollow heterostructures from metal-organic frameworks for stable Zn-ion storage. Angew. Chem., Int. Ed. 2021, 60, 25793–25798.

Crossref Google Scholar
18

Zhao, J. Q.; Xu, Z. J.; Zhou, Z.; Xi, S. B.; Xia, Y. P.; Zhang, Q. Y.; Huang, L. Q.; Mei, L.; Jiang, Y.; Gao, J. W. et al. A safe flexible self-powered wristband system by integrating defective MnO2−x nanosheet-based zinc-ion batteries with perovskite solar cells. ACS Nano 2021, 15, 10597–10608.

Crossref Google Scholar
19
. (a) Hao, Y.; Feng, D. D.; Hou, L.; Li, T. Y.; Jiao, Y. C.; Wu, P. Y. Gel electrolyte constructing Zn (002) deposition crystal plane toward highly stable Zn anode. Adv. Sci. 2022, 9, e2104832; (b) Wu, F.; Chen, N.; Chen, R. J.; Zhu, Q. Z.; Qian, J.; Li, L. “Liquid-in-solid” and “solid-in-liquid” electrolytes with high rate capacity and long cycling life for lithium-ion batteries. Chem. Mater. 2016, 28, 848–856.https://doi.org/10.1021/acs.chemmater.5b04278
Crossref
20

Guo, Z. Y.; Fu, X.; Zhang, Y. X.; Chen, K. Non-selective synthesis and controllable transformation of parallel MnO2 with hydrogen ions. CrystEngComm 2020, 22, 6101–6105.

Crossref Google Scholar
21

Liu, Y.; Wang, J.; Zeng, Y. X.; Liu, J.; Liu, X. Q.; Lu, X. H. Interfacial engineering coupled valence tuning of MoO3 cathode for high-capacity and high-rate fiber-shaped zinc-ion batteries. Small 2020, 16, e1907458.

Crossref Google Scholar
22

Qiu, W. D.; Zhou, Q. H.; Xiao, H. B.; Zhou, C.; He, W. T.; Li, Y.; Lu, X. H. Phosphate ion and oxygen defect-modulated nickel cobaltite nanowires: A bifunctional cathode for flexible hybrid supercapacitors and microbial fuel cells. J. Mater. Chem. A 2020, 8, 8722–8730.

Crossref Google Scholar
23

Nai, J. W.; Lou, X. W. Hollow structures based on prussian blue and its analogs for electrochemical energy storage and conversion. Adv. Mater. 2019, 31, e1706825.

Crossref Google Scholar
24

Han, M. M.; Huang, J. W.; Liang, S. Q.; Shan, L. T.; Xie, X. S.; Yi, Z. Y.; Wang, Y. R.; Guo, S.; Zhou, J. Oxygen defects in β-MnO2 enabling high-performance rechargeable aqueous zinc/manganese dioxide battery. iScience 2020, 23, 100797.

Crossref Google Scholar
25

Liang, X.; Hart, C.; Pang, Q.; Garsuch, A.; Weiss, T.; Nazar, L. F. A highly efficient polysulfide mediator for lithium-sulfur batteries. Nat. Commun. 2015, 6, 5682.

Crossref Google Scholar
26

Zhang, X. W.; Meng, F.; Mao, S.; Ding, Q.; Shearer, M. J.; Faber, M. S.; Chen, J. H.; Hamers, R. J.; Jin, S. Amorphous MoSxCly electrocatalyst supported by vertical graphene for efficient electrochemical and photoelectrochemical hydrogen generation. Energy Environ. Sci. 2015, 8, 862–868.

Crossref Google Scholar
27

Zhang, Y.; Deng, S. J.; Luo, M.; Pan, G. X.; Zeng, Y. X.; Lu, X. H.; Ai, C. Z.; Liu, Q.; Xiong, Q. Q.; Wang, X. L. 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, 15, e1905452.

Crossref Google Scholar
28

Fang, G. Z.; Zhu, C. Y.; Chen, M. H.; Zhou, J.; Tang, B. Y.; Cao, X. X.; Zheng, X. S.; Pan, A. Q.; Liang, S. Q. Suppressing manganese dissolution in potassium manganate with rich oxygen defects engaged high-energy-density and durable aqueous zinc-ion battery. Adv. Funct. Mater. 2019, 29, 1808375.

Crossref Google Scholar
29

Chen, L. L.; Yang, Z. H.; Qin, H. G.; Zeng, X.; Meng, J. L.; Chen, H. Z. Graphene-wrapped hollow ZnMn2O4 microspheres for high-performance cathode materials of aqueous zinc ion batteries. Electrochim. Acta 2019, 317, 155–163.

Crossref Google Scholar
30

Huang, C.; Wang, Q. F.; Tian, G. F.; Zhang, D. H. Oxygen vacancies-enriched Mn3O4 enabling high-performance rechargeable aqueous zinc-ion battery. Mater. Today Phys. 2021, 21, 100518.

Crossref Google Scholar
31

Soundharrajan, V.; Sambandam, B.; Kim, S.; Islam, S.; Jo, J.; Kim, S.; Mathew, V.; Sun, Y. K.; Kim, J. The dominant role of Mn2+ additive on the electrochemical reaction in ZnMn2O4 cathode for aqueous zinc-ion batteries. Energy Storage Mater. 2020, 28, 407–417.

Crossref Google Scholar
32

Wu, Y.; Fee, J.; Tobin, Z.; Shirazi-Amin, A.; Kerns, P.; Dissanayake, S.; Mirich, A.; Suib, S. L. Amorphous manganese oxides: An approach for reversible aqueous zinc-ion batteries. ACS Appl. Energy Mater. 2020, 3, 1627–1633.

Crossref Google Scholar
33

Shi, M. J.; Wang, B.; Shen, Y.; Jiang, J. T.; Zhu, W. H.; Su, Y. J.; Narayanasamy, M.; Angaiah, S.; Yan, C.; Peng, Q. 3D assembly of MXene-stabilized spinel ZnMn2O4 for highly durable aqueous zinc-ion batteries. Chem. Eng. J. 2020, 399, 125627.

Crossref Google Scholar
34

Chen, L. L.; Yang, Z. H.; Qin, H. G.; Zeng, X.; Meng, J. L. Advanced electrochemical performance of ZnMn2O4/N-doped graphene hybrid as cathode material for zinc ion battery. J. Power Sources 2019, 425, 162–169.

Crossref Google Scholar
35

Li, X. J.; Tang, Y. C.; Zhu, J. X.; Lv, H. M.; Zhao, L. M.; Wang, W. L.; Zhi, C. Y.; Li, H. F. Boosting the cycling stability of aqueous flexible Zn batteries via F doping in nickel-cobalt carbonate hydroxide cathode. Small 2020, 16, e2001935.

Crossref Google Scholar
36

Wang, S. Z.; Li, L. L.; He, W. D.; Shao, Y. L.; Li, Y. L.; Wu, Y. Z.; Hao, X. P. Oxygen vacancy modulation of bimetallic oxynitride anodes toward advanced Li-ion capacitors. Adv. Funct. Mater. 2020, 30, 2000350.

Crossref Google Scholar
37

Wang, S. Z.; Zhao, H. P.; Lv, S. Y.; Jiang, H. H.; Shao, Y. L.; Wu, Y. Z.; Hao, X. P.; Lei, Y. Insight into nickel-cobalt oxysulfide nanowires as advanced anode for sodium-ion capacitors. Adv. Energy Mater. 2021, 11, 2100408.

Crossref Google Scholar
38

Wang, J. J.; Wang, J. G.; Liu, H. Y.; Wei, C. G.; Kang, F. Y. Zinc ion stabilized MnO2 nanospheres for high capacity and long lifespan aqueous zinc-ion batteries. J. Mater. Chem. A 2019, 7, 13727–13735.

Crossref Google Scholar
39

Li, H. F.; Yang, Q.; Mo, F. N.; Liang, G. J.; Liu, Z. X.; Tang, Z. J.; Ma, L. T.; Liu, J.; Shi, Z. C.; Zhi, C. Y. MoS2 nanosheets with expanded interlayer spacing for rechargeable aqueous Zn-ion batteries. Energy Storage Mater. 2019, 19, 94–101.

Crossref Google Scholar
40

Zhang, B. H.; Liu, Y.; Wu, X. W.; Yang, Y. Q.; Chang, Z.; Wen, Z. B.; Wu, Y. P. An aqueous rechargeable battery based on zinc anode and Na0.95MnO2. Chem. Commun. 2014, 50, 1209–1211.

Crossref Google Scholar
41

Li, W.; Wang, K. L.; Cheng, S. J.; Jiang, K. A long-life aqueous Zn-ion battery based on Na3V2(PO4)2F3 cathode. Energy Storage Mater. 2018, 15, 14–21.

Crossref Google Scholar
Nano Research
Volume 15 Issue 9,
September 2022
Pages 8118-8127
DOI: 10.1007/s12274-022-4498-9
Cite this article:
Huang C, Wang Q, Zhang D, et al. Coupling N-doping and rich oxygen vacancies in mesoporous ZnMn2O4 nanocages toward advanced aqueous zinc ion batteries. Nano Research, 2022, 15(9): 8118-8127. https://doi.org/10.1007/s12274-022-4498-9
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