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SCIENCE CHINA Materials, Volume 60, Issue 5: 415-426(2017) https://doi.org/10.1007/s40843-017-9021-6

Long life rechargeable Li-O2 batteries enabled by enhanced charge transfer in nanocable-like Fe@N-doped carbon nanotube catalyst

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  • ReceivedFeb 22, 2017
  • AcceptedMar 24, 2017
  • PublishedApr 12, 2017

Abstract

Rechargeable Li-O2 batteries have attracted considerable interests because of their exceptional energy density. However, the short lifetime still remained as one of the bottle-neck obstacles for the practical application of rechargeable Li-O2 batteries. The development of efficient cathode catalyst is highly desirable to reduce the energy barrier of Li-O2 reaction and electrode failure. In this work, we report a facile strategy for the fabrication of a high-performance cathode catalyst for rechargeable Li-O2 batteries by the encapsulation of high content of active Fe nanorods into N-doped carbon nanotubes with high stability (denoted as Fe@NCNTs). First-principles calculations reveal that the synergistic charge transfer and redistribution between the interface of Fe nanorods, the CNT walls and the active N dopants greatly facilitate the chemisorption and subsequent dissociation of O2 molecules into the epoxy intermediates on the carbon surface, which benefits the uniform growth of nanosized discharge products on CNT surface and thus boosts the reversibility of Li-O2 reactions. As a result, the cathode with Fe@NCNT catalyst exhibits long cycling stability with high capacities (1000 mA h g−1 for 160 cycles and 600 mA h g−1 for 270 cycles). Based on the total mass of Fe@NCNTs + Li2O2, high gravimetric energy densities of 2120–2600 W h kg−1 can be achieved at the power densities of 50–795 W kg−1.


Funded by

National Natural Science Foundation of China(NSFC,51522203)

Fok Ying Tung Education Foundation(151047)

Recruitment Program of Global Youth Experts(2014)

Xinghai Scholarship of Dalian University of Technology

and the Opening Project of State Key Lab of Polymer Materials Engineering

China(Sklpme2015-4-25)


Acknowledgment

This work was supported by the National Natural Science Foundation of China (NSFC, 51522203), Fok Ying Tung Education Foundation (151047), the Recruitment Program of Global Youth Experts (2014) and Xinghai Scholarship of Dalian University of Technology. Wang Z and Zhou T also acknowledge the support by the Opening Project of State Key Lab of Polymer Materials Engineering, China (Sklpme2015-4-25).


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Wang Z and Qiu J directed and designed the project. Yu M performed the experiments. Liu Y, Zhao Z and Zhou T contributed to the strategy optimization. Wang Z and Yu M analyzed the results and wrote the paper. Zhou S and Zhao J performed the DFT calculation. All authors contributed to the general discussion.


Author information

Mengzhou Yu received her MSc degree from Dalian University of Technology (DUT) in 2016. Currently, she is a PhD candidate at the School of Chemical Engineering in DUT. Her research mainly focuses on the development of high-performance electrocatalysts for oxygen reduction/evolution reactions.


Si Zhou received her PhD degree from the School of Physics at Georgia Institute of Technology in 2014. She is currently an associate professor at DUT. Her research interests focus on computational design of advanced materials for electronics and energy storage and conversion devices.


Zhiyu Wang received his PhD degree from the School of Chemical Engineering at DUT in China. Currently he is a professor of the School of Chemical Engineering in DUT. His research focuses on the design and synthesis of functional hybrid nanomaterials for energy storage/conversion applications.


Jieshan Qiu received his PhD degree from the School of Chemical Engineering at DUT in China. He was appointed to a Cheung-Kong Distinguished Professor in 2009. He is a professor of the School of Chemical Engineering and director of the Carbon Research Laboratory at DUT. His research focuses on the development of new methodologies for the synthesis of functional carbon materials, as well as their applications in catalysis, energy conversion/storage and environment protection.


Supplement

Supplementary information

Supporting data are available in the online version of the paper.


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  • Figure 1

    (a, b) FESEM images of the Fe@NCNT sample; (c) elemental mapping showing the uniform distribution of C, Fe and N element; (d, e) TEM images of Fe@NCNTs; (f) HRTEM image revealing the single crystalline nature of Fe nanorods within CNT shells with a high degree of graphitization.

  • Figure 2

    (a) XRD pattern, (b) XPS full scan spectrum and (c) N 1s XPS spectrum of Fe@NCNT sample; (d) nitrogen-adsorption-desorption isotherm and pores size distribution of Fe@NCNT sample.

  • Figure 3

    (a) The discharge-charge voltage curves of the Fe@NCNT, CNT and carbon black electrodes at a current density of 100 mA g−1; (b) the discharge-charge voltage curves of the Fe@NCNT electrodes at varied current densities of 100, 500 and 1000 mA g−1. (c) Gravimetric Ragone plot comparing energy and power characteristics of the Fe@NCNT electrodes with other energy storage technologies. (d) Cycling performance of the Fe@NCNT, NCNT, CNT and carbon black electrodes with a restricted capacity of 600 and 1000 mA h g−1; (e) the discharge-charge voltage curves of the Fe@NCNT electrodes with a restricted capacity of 1000 mA h g−1 for the 1st, 20th, 50th, 100th and 160th cycles; (f) the discharge-charge voltage curves of the Fe@NCNT, NCNT, CNT and carbon black electrodes with a restricted capacity of 1000 mA h g−1 at 200 mA g−1.

  • Figure 4

    (a) XRD patterns of the fresh, discharged and recharged Fe@NCNT electrodes; (b, c, d) SEM images of the fresh, fully discharged and fully charged Fe@NCNT electrodes, respectively.

  • Figure 5

    (a) A slab model of Fe@NCNTs for DFT calculation; (b, c, d) the structural models of Fe@CNTs doped with pyridinic-N, graphitic-N and pyrrolic-N, respectively. The grey, blue, pink and purple spheres represent the C, N, the top-layer Fe and the bottom-layer Fe atoms in the models, respectively.

  • Figure 6

    Energy diagrams of the reaction pathway for the adsorption of O2 molecule on (a) Fe@CNTs, (b) Fe@pyridinic-N doped CNTs, (c) Fe@graphitic-N doped CNTs, (d) Fe@pyrrolic-N doped CNTs. The grey, blue, red, pink and purple spheres represent C, N, O, and the top layer Fe atoms in the models, respectively. The structures above red line are the transition states.

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