Simultaneous growth of carbon nanotubes on inner/outer surfaces of porous polyhedra: Advanced sulfur hosts for lithium-sulfur batteries
- 338 Downloads
Metal-organic framework (MOF)-derived functional carbon matrices have recently attracted considerable attention as energy-storage materials. However, the development of MOF-derived carbon materials with hierarchical structures, capable of thoroughly preventing the “shuttling᾿of polysulfides, is still a major challenge. Herein, we synthesized cobalt nanoparticle-containing porous carbon polyhedra with in situ grown N-doped carbon nanotube (CNT) backbone (NCCNT-Co), using zeolitic imidazolate framework-67 (ZIF-67) as starting material. The obtained NCCNT-Co, with interconnected N-doped CNTs on both inner and outer surfaces, possesses an integrated conductive network, which can further accelerate the transport of electrons/ions inside the whole sulfur cathode. The mesoporous structure derived from the ZIF-67 matrix and the densely immobilized CNTs, coupled with the homogeneously doped N atoms and Co nanoparticles, can efficiently trap lithium polysulfides (LiPSs) by physical confinement and chemical interactions. Furthermore, the hierarchical structure of the porous carbon polyhedra enables a high sulfur loading of up to 76 wt.% and can also buffer the volume changes of active sulfur during the lithiation process. As a result, the NCCNT-Co-S cathode delivers a high initial specific capacity of 1,300 mAh·g−1 at 0.1 C, along with a high capacity of 860 mAh·g−1 after 500 cycles at 1 C, with an extremely low capacity decay of 0.024% per cycle.
Keywordszeolitic imidazolate framework-67 (ZIF-67) carbon nanotubes in situ growth Li-S batteries
Unable to display preview. Download preview PDF.
The authors are grateful for the financial support from the National Natural Science Foundation of China (Nos. 51433001 and 51373037), the Program of Shanghai Academic Research Leader (No. 17XD1400100), Natural Science Foundation of Jiangsu Province (No. BK20150238), and the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.
- Li, Y. J.; Fan, J. M.; Zheng, M. S.; Dong, Q. F. A novel synergistic composite with multi-functional effects for high-performance Li-S batteries. Energy Environ. Sci. 2016, 9, 1998–2004.Google Scholar
- Peng, H. J.; Huang, J. Q.; Zhao, M. Q.; Zhang, Q.; Cheng, X. B.; Liu, X. Y.; Qian, W. Z.; Wei, F. Nanoarchitectured graphene/CNT@porous carbon with extraordinary electrical conductivity and interconnected micro/mesopores for lithiumsulfur batteries. Adv. Funct. Mater. 2014, 24, 2772–2781.CrossRefGoogle Scholar
- Zhu, L.; Peng, H. J.; Liang, J. Y.; Huang, J. Q.; Chen, C. M.; Guo, X. F.; Zhu, W. C.; Li, P.; Zhang, Q. Interconnected carbon nanotube/graphene nanosphere scaffolds as freestanding paper electrode for high-rate and ultra-stable lithium–sulfur batteries. Nano Energy 2015, 11, 746–755.CrossRefGoogle Scholar
- Song, J. X.; Xu, T.; Gordin, M. L.; Zhu, P. Y.; Lv, D. P.; Jiang, Y. B.; Chen, Y. S.; Duan, Y. H.; Wang, D. H. Nitrogen-doped mesoporous carbon promoted chemical adsorption of sulfur and fabrication of high-areal-capacity sulfur cathode with exceptional cycling stability for lithiumsulfur batteries. Adv. Funct. Mater. 2014, 24, 1243–1250.CrossRefGoogle Scholar
- Xiao, Z. B.; Yang, Z.; Wang, L.; Nie, H. G.; Zhong, M. E.; Lai, Q. Q.; Xu, X. J.; Zhang, L. J.; Huang, S. M. A lightweight TiO2/graphene interlayer, applied as a highly effective polysulfide absorbent for fast, long-life lithium-sulfur batteries. Adv. Mater. 2015, 27, 2891–2898.CrossRefGoogle Scholar
- Li, Z. Q.; Li, C. X.; Ge, X. L.; Ma, J. Y.; Zhang, Z. W.; Li, Q.; Wang, C. X.; Yin, L. W. Reduced graphene oxide wrapped MOFs-derived cobalt-doped porous carbon polyhedrons as sulfur immobilizers as cathodes for high performance lithium sulfur batteries. Nano Energy 2016, 23, 15–26.CrossRefGoogle Scholar
- Qiu, Y. C.; Li, G. Z.; Hou, Y.; Pan, Z. H.; Li, H. F.; Li, W. F.; Liu, M. N.; Ye, F. M.; Yang, X. W.; Zhang, Y. G. Vertically aligned carbon nanotubes on carbon nanofibers: A hierarchical three-dimensional carbon nanostructure for high-energy flexible supercapacitors. Chem. Mater. 2015, 27, 1194–1200.CrossRefGoogle Scholar
- Gulzar, U.; Li, T.; Bai, X.; Colombo, M.; Ansaldo, A.; Marras, S.; Prato, M.; Goriparti, S.; Capiglia, C.; Proietti Zaccaria, R. Nitrogen-doped single-walled carbon nanohorns as a cost-effective carbon host toward high-performance lithium-sulfur batteries. ACS Appl. Mater. Interfaces 2018, 10, 5551–5559.CrossRefGoogle Scholar
- Song, J. X.; Gordin, M. L.; Xu, T.; Chen, S. R.; Yu, Z. X.; Sohn, H.; Lu, J.; Ren, Y.; Duan, Y. H.; Wang, D. H. Strong lithium polysulfide chemisorption on electroactive sites of nitrogen-doped carbon composites for high-performance lithium-sulfur battery cathodes. Angew. Chem., Int. Ed. 2015, 54, 4325–4329.CrossRefGoogle Scholar
- Chen, T.; Cheng, B. R.; Zhu, G. Y.; Chen, R. P.; Hu, Y.; Ma, L. B.; Lv, H. L.; Wang, Y. R.; Liang, J.; Tie, Z. X. et al. Highly efficient retention of polysulfides in “sea urchin᾿like carbon nanotube/nanopolyhedra superstructures as cathode material for ultralong-life lithium-sulfur batteries. Nano Lett. 2017, 17, 437–444.CrossRefGoogle Scholar
- Tang, C.; Zhang, Q.; Zhao, M. Q.; Huang, J. Q.; Cheng, X. B.; Tian, G. L.; Peng, H. J.; Wei, F. Nitrogen-doped aligned carbon nanotube/graphene sandwiches: Facile catalytic growth on bifunctional natural catalysts and their applications as scaffolds for high-rate lithium-sulfur batteries. Adv. Mater. 2014, 26, 6100–6105.CrossRefGoogle Scholar