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Nano Research 2019, 12(10): 2528-2534 https://doi.org/10.1007/s12274-019-2480-y
Research Article | Issue | Published: 03 August 2019

Spatially-controlled porous nanoflake arrays derived from MOFs: An efficiently long-life oxygen electrode

Show Author's Information Hao Gong1,2,  Tao Wang1( ),  Hairong Xue1,  Xueyi Lu3,  Wei Xia1,  Li Song1,  Songtao Zhang4,  Jianping He1( ),  Renzhi Ma2( )
College of Materials Science and Technology,Jiangsu Key Laboratory of Materials and Technology for Energy Conversion, Nanjing University of Aeronautics and Astronautics,Nanjing,210016,China;
International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba,Ibaraki,305-0044,Japan;
School of Chemistry and Chemical Engineering,South China University of Technology, Wushan Road 381,Guangzhou,510641,China;
Testing Center,Yangzhou University,Yangzhou,225009,China;
Keywords:
two-dimension metal-organic frameworks, mesoporous Co3O4, flexible oxygen electrode, lithium-oxygen batteries
Topics:
Air batteriesCathodesCrystalline materials Energy storageLithiumMorphologyOrganometallicsOxygen
Cite this article:
Gong H, Wang T, Xue H, et al. Spatially-controlled porous nanoflake arrays derived from MOFs: An efficiently long-life oxygen electrode. Nano Research, 2019, 12(10): 2528-2534. https://doi.org/10.1007/s12274-019-2480-y
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Abstract Full text Electronic supplementary material About this article

The urgent expectation of the next-generation energy storage devices for electric vehicles has driven researchers' attention to the lithium-oxygen (Li-O2) batteries due to the satisfied specific energy density. Herein, spatially-controlled Co3O4 nanoflake arrays with three-dimensional- networked morphology are adopted as flexible and self-standing oxygen cathodes in Li-O2 batteries. The spinel-phase Co3O4 nanoflakes were converted from two-dimension metal-organic frameworks with abundant available channels and large specific surface area. The open-structure nanoflake arrays possess sufficient Li2O2/cathode contact interface, great bifunctional catalytic performance and adequate Li2O2 accommodation, leading to the enhanced electrochemical performance of the Li-O2 batteries. As expected, the binder-free porous Co3O4/CT cathode delivers a high capacity of 6, 509 mAh·g-1 (200 mA·g-1) and enhanced stability over 100 cycles (limited by 1, 000 mAh·g-1). In addition, pouch-type Li-O2 batteries were successfully designed and cycled with Co3O4/CT cathode as oxygen electrodes, demonstrating its potential application for flexible electronics and wearable energy storage devices.


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Electronic supplementary material
About this article

Spatially-controlled porous nanoflake arrays derived from MOFs: An efficiently long-life oxygen electrode

Show Author's information Hao Gong1,2, Tao Wang1( ), Hairong Xue1, Xueyi Lu3, Wei Xia1, Li Song1, Songtao Zhang4, Jianping He1( ), Renzhi Ma2( )
College of Materials Science and Technology,Jiangsu Key Laboratory of Materials and Technology for Energy Conversion, Nanjing University of Aeronautics and Astronautics,Nanjing,210016,China;
International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba,Ibaraki,305-0044,Japan;
School of Chemistry and Chemical Engineering,South China University of Technology, Wushan Road 381,Guangzhou,510641,China;
Testing Center,Yangzhou University,Yangzhou,225009,China;

Abstract

The urgent expectation of the next-generation energy storage devices for electric vehicles has driven researchers' attention to the lithium-oxygen (Li-O2) batteries due to the satisfied specific energy density. Herein, spatially-controlled Co3O4 nanoflake arrays with three-dimensional- networked morphology are adopted as flexible and self-standing oxygen cathodes in Li-O2 batteries. The spinel-phase Co3O4 nanoflakes were converted from two-dimension metal-organic frameworks with abundant available channels and large specific surface area. The open-structure nanoflake arrays possess sufficient Li2O2/cathode contact interface, great bifunctional catalytic performance and adequate Li2O2 accommodation, leading to the enhanced electrochemical performance of the Li-O2 batteries. As expected, the binder-free porous Co3O4/CT cathode delivers a high capacity of 6, 509 mAh·g-1 (200 mA·g-1) and enhanced stability over 100 cycles (limited by 1, 000 mAh·g-1). In addition, pouch-type Li-O2 batteries were successfully designed and cycled with Co3O4/CT cathode as oxygen electrodes, demonstrating its potential application for flexible electronics and wearable energy storage devices.

Keywords: two-dimension metal-organic frameworks, mesoporous Co3O4, flexible oxygen electrode, lithium-oxygen batteries

References(52)

1

Ma, Z.; Yuan, X. X.; Li, L.; Ma, Z. F.; Wilkinson, D. P.; Zhang, L.; Zhang, J. J. A review of cathode materials and structures for rechargeable lithium-air batteries. Energy Environ. Sci. 2015, 8, 2144-2198.
DOI Google Scholar
2

Bruce, P. G.; Freunberger, S. A.; Hardwick, L. J.; Tarascon, J. M. Li-O2 and Li-S batteries with high energy storage. Nat. Mater. 2012, 11, 19-29.
DOI Google Scholar
3

Yu, L.; Hu, H.; Wu, H. B.; Lou, X. W. Complex hollow nanostructures: Synthesis and energy-related applications. Adv. Mater. 2017, 29, 1604563.
DOI Google Scholar
4

Gong, H.; Wang, T.; Xue, H. R.; Fan, X. L.; Gao, B.; Zhang, H. B.; Shi, L.; He, J. P.; Ye, J. H. Photo-enhanced lithium oxygen batteries with defective titanium oxide as both photo-anode and air electrode. Energy Storage Mater. 2018, 13, 49-56.
DOI Google Scholar
5

Wu, S. C.; Yi, J.; Zhu, K.; Bai, S. Y.; Liu, Y.; Qiao, Y.; Ishida, M.; Zhou, H. S. A super-hydrophobic quasi-solid electrolyte for Li-O2 battery with improved safety and cycle life in humid atmosphere. Adv. Energy Mater. 2017, 7, 1601759.
DOI Google Scholar
6

Wang, Z. L.; Xu, D.; Xu, J. J.; Zhang, X. B. Oxygen electrocatalysts in metal-air batteries: From aqueous to nonaqueous electrolytes. Chem. Soc. Rev. 2014, 43, 7746-7786.
DOI Google Scholar
7

Chang, Z. W.; Xu, J. J.; Zhang, X. B. Recent progress in electrocatalyst for Li-O2 batteries. Adv. Energy Mater. 2017, 7, 1700875.
DOI Google Scholar
8

Xue, H. R.; Wu, S. C.; Tang, J.; Gong, H.; He, P.; He, J. P.; Zhou, H. S. Hierarchical porous nickel cobaltate nanoneedle arrays as flexible carbon-protected cathodes for high-performance lithium-oxygen batteries. ACS Appl. Mater. Interfaces 2016, 8, 8427-8435.
DOI Google Scholar
9

Thackeray, M. M.; Wolverton, C.; Isaacs, E. D. Electrical energy storage for transportation〞approaching the limits of, and going beyond, lithium-ion batteries. Energy Environ. Sci. 2012, 5, 7854-7863.
DOI Google Scholar
10

Armand, M.; Tarascon, J. M. Building better batteries. Nature 2008, 451, 652-657.
DOI Google Scholar
11

Padbury, R.; Zhang, X. W. Lithium-oxygen batteries〞limiting factors that affect performance. J. Power Sources 2011, 196, 4436-4444.
DOI Google Scholar
12

Gong, H.; Xue, H. R.; Wang, T.; Guo, H.; Fan, X. L.; Song, L.; Xia, W.; He, J. P. High-loading nickel cobaltate nanoparticles anchored on three- dimensional N-doped graphene as an efficient bifunctional catalyst for lithium-oxygen batteries. ACS Appl. Mater. Interfaces 2016, 8, 18060-18068.
DOI Google Scholar
13

Chen, L. Y.; Guo, X. W.; Han, J. H.; Liu, P.; Xu, X. D.; Hirata, A.; Chen, M. W. Nanoporous metal/oxide hybrid materials for rechargeable lithium- oxygen batteries. J. Mater. Chem. A 2015, 3, 3620-3626.
DOI Google Scholar
14

Lu, X. Y.; Yin, Y.; Zhang, L.; Huang, S. Z.; Xi, L. X.; Liu, L. X.; Oswald, S.; Schmidt, O. G. 3D Ag/NiO-Fe2O3/Ag nanomembranes as carbon-free cathode materials for Li-O2 batteries. Energy Storage Mater. 2019, 16, 155-162.
DOI Google Scholar
15

Sun, C. W.; Li, F.; Ma, C.; Wang, Y.; Ren, Y. L.; Yang, W.; Ma, Z. H.; Li, J. Q.; Chen, Y. J.; Kim, Y. et al. Graphene-Co3O4 nanocomposite as an efficient bifunctional catalyst for lithium-air batteries. J. Mater. Chem. A 2014, 2, 7188-7196.
DOI Google Scholar
16

Sun, B.; Huang, X. D.; Chen, S. Q.; Munroe, P.; Wang, G. X. Porous graphene nanoarchitectures: An efficient catalyst for low charge-overpotential, long life, and high capacity lithium-oxygen batteries. Nano Lett. 2014, 14, 3145-3152.
DOI Google Scholar
17

Jian, Z. L.; Liu, P.; Li, F. J.; He, P.; Guo, X. W.; Chen, M. W.; Zhou, H. S. Core-shell-structured CNT@RuO2 composite as a high-performance cathode catalyst for rechargeable Li-O2 batteries. Angew. Chem., Int. Ed. 2014, 53, 442-446.
DOI Google Scholar
18

Li, F. J.; Zhang, T.; Yamada, Y.; Yamada, A.; Zhou, H. S. Enhanced cycling performance of Li-O2 batteries by the optimized electrolyte concentration of LiTFSA in glymes. Adv. Energy Mater. 2013, 3, 532-538.
DOI Google Scholar
19

Zhu, Z.; Kushima, A.; Yin, Z. Y.; Qi, L.; Amine, K.; Lu, J.; Li, J. Anion- redox nanolithia cathodes for Li-ion batteries. Nat. Energy 2016, 1, 16111.
DOI Google Scholar
20

McCloskey, B. D.; Addison, D. A viewpoint on heterogeneous electrocatalysis and redox mediation in nonaqueous Li-O2 batteries. ACS Catal. 2017, 7, 772-778.
DOI Google Scholar
21

Xia, W.; Mahmood, A.; Liang, Z. B.; Zou, R. Q.; Guo, S. J. Earth-abundant nanomaterials for oxygen reduction. Angew. Chem., Int. Ed. 2016, 55, 2650-2676.
DOI Google Scholar
22

Zhao, Q.; Yan, Z. H.; Chen, C. C.; Chen, J. Spinels: Controlled preparation, oxygen reduction/evolution reaction application, and beyond. Chem. Rev. 2017, 117, 10121-10211.
DOI Google Scholar
23

Lu, X. Y.; Deng, J. W.; Si, W. P.; Sun, X. L.; Liu, X. H.; Liu, B.; Liu, L. F.; Oswald, S.; Baunack, S.; Grafe, H. J. et al. High-performance Li-O2 batteries with trilayered Pd/MnOx/Pd nanomembranes. Adv. Sci. 2015, 2, 1500113.
DOI Google Scholar
24

Xia, B. Y.; Yan, Y.; Li, N.; Wu, H. B.; Lou, X. W.; Wang, X. A metal-organic framework-derived bifunctional oxygen electrocatalyst. Nat. Energy 2016, 1, 15006.
DOI Google Scholar
25

Yin, W.; Shen, Y.; Zou, F.; Hu, X. L.; Chi, B.; Huang, Y. H. Metal-organic framework derived ZnO/ZnFe2O4/C nanocages as stable cathode material for reversible lithium-oxygen batteries. ACS Appl. Mater. Interfaces 2015, 7, 4947-4954.
DOI Google Scholar
26

Huang, T.; Chen, Y.; Lee, J. A microribbon hybrid structure of CoOx-MoC encapsulated in N-doped carbon nanowire derived from MOF as efficient oxygen evolution electrocatalysts. Small 2017, 13, 17023.
DOI Google Scholar
27

Hou, Y.; Huang, T. Z.; Wen, Z. H.; Mao, S.; Cui, S. M.; Chen, J. H. Metal-organic framework-derived nitrogen-doped core-shell-structured porous Fe/Fe3C@C nanoboxes supported on graphene sheets for efficient oxygen reduction reactions. Adv. Energy Mater. 2014, 4, 1400337.
DOI Google Scholar
28

Jia, G.; Zhang, W.; Fan, G. Z.; Li, Z. S.; Fu, D. G.; Hao, W. C.; Yuan, C. W.; Zou, Z. G. Three-dimensional hierarchical architectures derived from surface-mounted metal-organic framework membranes for enhanced electrocatalysis. Angew. Chem., Int. Ed. 2017, 56, 13781-13785.
DOI Google Scholar
29

Tang, J.; Wu, S. C.; Wang, T.; Gong, H.; Zhang, H. B.; Alshehri, S. M.; Ahamad, T.; Zhou, H. S.; Yamauchi, Y. Cage-type highly graphitic porous carbon-Co3O4 polyhedron as the cathode of lithium-oxygen batteries. ACS Appl. Mater. Interfaces 2016, 8, 2796-2804.
DOI Google Scholar
30

Wu, D. F.; Guo, Z. Y.; Yin, X. B.; Pang, Q. Q.; Tu, B. B.; Zhang, L. J.; Wang, Y. G.; Li, Q. W. Metal-organic frameworks as cathode materials for Li-O2 batteries. Adv. Mater. 2014, 26, 3258-3262.
DOI Google Scholar
31

Li, Q.; Xu, P.; Gao, W.; Ma, S. G.; Zhang, G. Q.; Cao, R. G.; Cho, J.; Wang, H. L.; Wu, G. Graphene/graphene-tube nanocomposites templated from cage-containing metal-organic frameworks for oxygen reduction in Li-O2 batteries. Adv. Mater. 2014, 26, 1378-1386.
DOI Google Scholar
32

Zhang, J.; Wang, L. J.; Xu, L. L.; Ge, X. M.; Zhao, X.; Lai, M.; Liu, Z. L.; Chen, W. Porous cobalt-manganese oxide nanocubes derived from metal organic frameworks as a cathode catalyst for rechargeable Li-O2 batteries. Nanoscale 2015, 7, 720-726.
DOI Google Scholar
33

Wu, F.; Zhang, X. X.; Zhao, T. L.; Chen, R. J.; Ye, Y. S.; Xie, M.; Li, L. Hierarchical mesoporous/macroporous Co3O4 ultrathin nanosheets as free-standing catalysts for rechargeable lithium-oxygen batteries. J. Mater. Chem. A 2015, 3, 17620-17626.
DOI Google Scholar
34

Riaz, A.; Jung, K. N.; Chang, W.; Lee, S. B.; Lim, T. H.; Park, S. J.; Song, R. H.; Yoon, S.; Shin, K. H.; Lee, J. W. Carbon-free cobalt oxide cathodes with tunable nanoarchitectures for rechargeable lithium-oxygen batteries. Chem. Commun. 2013, 49, 5984-5986.
DOI Google Scholar
35

Liu, Q. C.; Xu, J. J.; Chang, Z. W.; Zhang, X. B. Direct electrodeposition of cobalt oxide nanosheets on carbon paper as free-standing cathode for Li-O2 battery. J. Mater. Chem. A 2014, 2, 6081-6085.
DOI Google Scholar
36

Guan, C.; Sumboja, A.; Wu, H. J.; Ren, W. N.; Liu, X. M.; Zhang, H.; Liu, Z. L.; Cheng, C. W.; Pennycook, S. J.; Wang, J. Hollow Co3O4 nanosphere embedded in carbon arrays for stable and flexible solid-state zinc-air batteries. Adv. Mater. 2017, 29, 1704117.
DOI Google Scholar
37

Guan, C.; Liu, X. M.; Ren, W. N.; Li, X.; Cheng, C. W.; Wang, J. Rational design of metal-organic framework derived hollow NiCo2O4 arrays for flexible supercapacitor and electrocatalysis. Adv. Energy Mater. 2017, 7, 1602391.
DOI Google Scholar
38

Chen, R. Z.; Yao, J. F.; Gu, Q. F.; Smeets, S.; Baerlocher, C.; Gu, H. X.; Zhu, D. R.; Morris, W.; Yaghi, O. M.; Wang, H. T. A two-dimensional zeolitic imidazolate framework with a cushion-shaped cavity for CO2 adsorption. Chem. Commun. 2013, 49, 9500-9502.
DOI Google Scholar
39

Wang, Z. L.; Xu, D.; Xu, J. J.; Zhang, L. L.; Zhang, X. B. Graphene oxide gel-derived, free-standing, hierarchically porous carbon for high-capacity and high-rate rechargeable Li-O2 batteries. Adv. Funct. Mater. 2012, 22, 3699-3705.
DOI Google Scholar
40

Guo, Z. Y.; Zhou, D. D.; Dong, X. L.; Qiu, Z. J.; Wang, Y. G.; Xia, Y. Y. Ordered hierarchical mesoporous/macroporous carbon: A high-performance catalyst for rechargeable Li-O2 batteries. Adv. Mater. 2013, 25, 5668-5672.
DOI Google Scholar
41

Varghese, B.; Teo, C. H.; Zhu, Y.; Reddy, M. V.; Chowdari, B. V. R.; Wee, A. T. S.; Tan, V. B. C.; Lim, C. T.; Sow, C. H. Co3O4 nanostructures with different morphologies and their field-emission properties. Adv. Funct. Mater. 2007, 17, 1932-1939.
DOI Google Scholar
42

Wu, Z. S.; Ren, W. C.; Wen, L.; Gao, L. B.; Zhao, J. P.; Chen, Z. P.; Zhou, G. M.; Li, F.; Cheng, H. M. Graphene anchored with Co3O4 nanoparticles as anode of lithium ion batteries with enhanced reversible capacity and cyclic performance. ACS Nano 2010, 4, 3187-3194.
DOI Google Scholar
43

Guan, Q.; Cheng, J. L.; Wang, B.; Ni, W.; Gu, G. F.; Li, X. D.; Huang, L.; Yang, G. C.; Nie, F. D. Needle-like Co3O4 anchored on the graphene with enhanced electrochemical performance for aqueous supercapacitors. ACS Appl. Mater. Interfaces 2014, 6, 7626-7632.
DOI Google Scholar
44

Wang, S. F.; Sha, Y. J.; Zhu, Y. L.; Xu, X. M.; Shao, Z. P. Modified template synthesis and electrochemical performance of a Co3O4/mesoporous cathode for lithium-oxygen batteries. J. Mater. Chem. A 2015, 3, 16132-16141.
DOI Google Scholar
45

Wu, R. B.; Qian, X. K.; Zhou, K.; Wei, J.; Lou, J.; Ajayan, P. M. Porous spinel ZnxCo3-xO4 hollow polyhedra templated for high-rate lithium-ion batteries. ACS Nano 2014, 8, 6297-6303.
DOI Google Scholar
46

Avci, C.; Imaz, I.; Carné-Sánchez, A.; Pariente, J. A.; Tasios, N.; Pérez- Carvajal, J.; Alonso, M. I.; Blanco, A.; Dijkstra, M.; López, C. et al. Self-assembly of polyhedral metal-organic framework particles into three- dimensional ordered superstructures. Nat. Chem. 2018, 10, 78-84.
DOI Google Scholar
47

Aijaz, A.; Masa, J.; Rösler, C.; Xia, W.; Weide, P.; Botz, A. J. R.; Fischer, R. A.; Schuhmann, W.; Muhler, M. Co@Co3O4 encapsulated in carbon nanotube-grafted nitrogen-doped carbon polyhedra as an advanced bifunctional oxygen electrode. Angew. Chem., Int. Ed. 2016, 55, 4087-4091.
DOI Google Scholar
48

Wu, S. C.; Qiao, Y.; Deng, H.; Zhou, H. S. A single ion conducting separator and dual mediator-based electrolyte for high-performance lithium-oxygen batteries with non-carbon cathodes. J. Mater. Chem. A 2018, 6, 9816-9822.
DOI Google Scholar
49

Liu, T.; Liu, Q. C.; Xu, J. J.; Zhang, X. B. Cable-type water-survivable flexible Li-O2 battery. Small 2016, 12, 3101-3105.
DOI Google Scholar
50

Zhang, T.; Matsuda, H.; Zhou, H. S. Gel-derived cation-π stacking films of carbon nanotube-graphene complexes as oxygen cathodes. ChemSusChem 2014, 7, 2845-2852.
DOI Google Scholar
51

Liu, L. L.; Wang, J.; Hou, Y. Y.; Chen, J.; Liu, H. K.; Wang, J. Z.; Wu, Y. P. Self-assembled 3D foam-like NiCo2O4 as efficient catalyst for lithium oxygen batteries. Small 2016, 12, 602-611.
DOI Google Scholar
52

Tan, P.; Chen, B.; Xu, H. R.; Cai, W. Z.; He, W.; Liu, M. L.; Shao, Z. P.; Ni, M. Co3O4 nanosheets as active material for hybrid Zn batteries. Small 2018, 14, 1800225.
DOI Google Scholar
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Publication history
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Acknowledgements

Publication history

Received: 07 May 2019
Revised: 11 June 2019
Accepted: 13 July 2019
Published: 03 August 2019
Issue date: October 2019

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Acknowledgements

Acknowledgements

The authors thank for the financial support from the National Natural Science Foundation of China (Nos. 51602153 and 11575084), the Natural Science Foundation of Jiangsu Province (No. BK20160795), Postgraduate Research & Practice Innovation Program of Jiangsu Province (No. KYCX18_0276), Zhejiang Provincial Natural Science Foundation of China under (No. LQ18B010005), the Fundamental Research Funds for the Central Universities (No. NE2018104), and a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD). G. H. also thanks the China Scholarship Council for financial support.

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