Graphical Abstract

Although promising strategies have been developed to resolve the critical drawbacks of lithium-sulfur (Li-S) batteries, the intractable issues including undesirable shuttling of polysulfides and sluggish redox reaction kinetics have still been unresolved thoroughly. Herein, a cobalt single-atom (CoSA) catalyst comprising of atomic Co distributed homogeneously within nitrogen (N)-doped porous carbon (Co-NPC) nanosphere is constructed and utilized as a separator coating in Li-S batteries. The Co-NPC exposes abundant active sites participating in sulfur redox reactions, and remarkable catalytic activity boosting the rapid polysulfide conversions. As a result, Li-S batteries with Co-NPC coating layer realize significantly enhanced specific capacity (1295 mAh·g−1 at 0.2 C), rate capability (753 mAh·g−1 at 3.0 C), and long-life cyclic stability (601 mAh·g−1 after 500 cycles at 1.0 C). Increasing the areal sulfur loading to 6.2 mg·cm−2, an extremely high areal capacity of 7.92 mAh·cm−2 is achieved. Further in situ X-ray diffraction, density functional theory calculations, and secondary ion mass spectrometry confirm the high catalytic capability of CoSA towards reversible polysulfide conversion. This study supplies new insights for adopting single-atom catalyst to upgrade the electrochemical performance of Li-S batteries.
Goodenough, J. B.; Park, K. S. The Li-ion rechargeable battery: A perspective. J. Am. Chem. Soc. 2013, 135, 1167–1176.
Etacheri, V.; Marom, R.; Elazari, R.; Salitra, G.; Aurbach, D. Challenges in the development of advanced Li-ion batteries: A review. Energy Environ. Sci. 2011, 4, 3243–3262.
Yabuuchi, N.; Kubota, K.; Dahbi, M.; Komaba, S. Research development on sodium-ion batteries. Chem. Rev. 2014, 114, 11636–11682.
Kang, Q.; Li, Y.; Zhuang, Z. C.; Wang, D. S.; Zhi, C. Y.; Jiang, P. K.; Huang, X. Y. Dielectric polymer based electrolytes for high-performance all-solid-state lithium metal batteries. J. Energy Chem. 2022, 69, 194–204.
Ma, L. B.; Qian, J.; Li, Y. T.; Cheng, Y. W.; Wang, S. Y.; Wang, Z. W.; Peng, C.; Wu, K. L.; Xu, J.; Manke, I. et al. Binary metal single atom electrocatalysts with synergistic catalytic activity toward high-rate and high areal-capacity lithium-sulfur batteries. Adv. Funct. Mater. 2022, 32, 2208666.
Zhang, E. H.; Hu, X.; Meng, L. Z.; Qiu, M.; Chen, J. X.; Liu, Y. J.; Liu, G. Y.; Zhuang, Z. C.; Zheng, X. B.; Zheng, L. R. et al. Single-atom yttrium engineering Janus electrode for rechargeable Na-S batteries. J. Am. Chem. Soc. 2022, 144, 18995–19007.
Li, X.; Guan, Q. H.; Zhuang, Z. C.; Zhang, Y. Z.; Lin, Y. H.; Wang, J.; Shen, C. Y.; Lin, H. Z.; Wang, Y. L.; Zhan, L. et al. Ordered mesoporous carbon grafted MXene catalytic heterostructure as Li-ion kinetic pump toward high-efficient sulfur/sulfide conversions for Li-S battery. ACS Nano 2023, 17, 1653–1662.
Hu, B.; Xu, J.; Fan, Z. J.; Xu, C.; Han, S. C.; Zhang, J. X.; Ma, L. B.; Ding, B.; Zhuang, Z. C.; Kang, Q. et al. Covalent organic framework based lithium-sulfur batteries: Materials, interfaces, and solid-state electrolytes. Adv. Energy Mater. 2023, 2203540.
Fang, R. P.; Zhao, S. Y.; Sun, Z. H.; Wang, D. W.; Cheng, H. M.; Li, F. More reliable lithium-sulfur batteries: Status, solutions and prospects. Adv. Mater. 2017, 29, 1606823.
Manthiram, A.; Chung, S. H.; Zu, C. X. Lithium-sulfur batteries: Progress and prospects. Adv. Mater. 2015, 27, 1980–2006.
Peng, H. J.; Huang, J. Q.; Cheng, X. B.; Zhang, Q. Review on high-loading and high-energy lithium-sulfur batteries. Adv. Energy Mater. 2017, 7, 1700260.
Pang, Q.; Liang, X.; Kwok, C. Y.; Nazar, L. F. Advances in lithium-sulfur batteries based on multifunctional cathodes and electrolytes. Nat. Energy 2016, 1, 16132.
Jeong, Y. C.; Kim, J. H.; Nam, S.; Park, C. R.; Yang, S. J. Rational design of nanostructured functional interlayer/separator for advanced Li-S batteries. Adv. Funct. Mater. 2018, 28, 1707411.
Yao, H. B.; Yan, K.; Li, W. Y.; Zheng, G. Y.; Kong, D. S.; Seh, Z. W.; Narasimhan, V. K.; Liang, Z.; Cui, Y. Improved lithium-sulfur batteries with a conductive coating on the separator to prevent the accumulation of inactive S-related species at the cathode–separator interface. Energy Environ. Sci. 2014, 7, 3381–3390.
Xu, J.; Tang, W. Q.; Yang, C.; Manke, I.; Chen, N.; Lai, F. L.; Xu, T.; An, S. H.; Liu, H. L.; Zhang, Z. L. et al. A highly conductive COF@CNT electrocatalyst boosting polysulfide conversion for Li-S chemistry. ACS Energy Lett. 2021, 6, 3053–3062.
Wei, Z. Z.; Zhang, N. X.; Feng, T.; Wu, F.; Zhao, T.; Chen, R. J. A copolymer microspheres-coated separator to enhance thermal stability of lithium-sulfur batteries. Chem. Eng. J. 2022, 430, 132678.
Li, W. H.; Yang, J. R.; Wang, D. S. Long-range interactions in diatomic catalysts boosting electrocatalysis. Angew. Chem., Int. Ed. 2022, 61, e202213318.
Jing, H. Y.; Zhu, P.; Zheng, X. B.; Zhang, Z. D.; Wang, D. S.; Li, Y. D. Theory-oriented screening and discovery of advanced energy transformation materials in electrocatalysis. Adv. Power Mater. 2022, 1, 100013.
Zhuang, Z. C.; Li, Y. H.; Yu, R. H.; Xia, L. X.; Yang, J. R.; Lang, Z. Q.; Zhu, J. X.; Huang, J. Z.; Wang, J. O.; Wang, Y. et al. Reversely trapping atoms from a perovskite surface for high-performance and durable fuel cell cathodes. Nat. Catal. 2022, 5, 300–310.
Xiong, Y.; Sun, W. M.; Han, Y. H.; Xin, P. Y.; Zheng, X. S.; Yan, W. S.; Dong, J. C.; Zhang, J.; Wang, D. S.; Li, Y. D. Cobalt single atom site catalysts with ultrahigh metal loading for enhanced aerobic oxidation of ethylbenzene. Nano Res. 2021, 14, 2418–2423.
Zhuang, Z. C.; Xia, L. X.; Huang, J. Z.; Zhu, P.; Li, Y.; Ye, C. L.; Xia, M. G.; Yu, R. H.; Lang, Z. Q.; Zhu, J. X. et al. Continuous modulation of electrocatalytic oxygen reduction activities of single-atom catalysts through p-n junction rectification. Angew. Chem., Int. Ed. 2023, 62, e202212335.
Xie, J.; Li, B. Q.; Peng, H. J.; Song, Y. W.; Zhao, M.; Chen, X.; Zhang, Q.; Huang, J. Q. Implanting atomic cobalt within mesoporous carbon toward highly stable lithium-sulfur batteries. Adv. Mater. 2019, 31, 1903813.
Ma, C.; Zhang, Y. Q.; Feng, Y. M.; Wang, N.; Zhou, L. J.; Liang, C. P.; Chen, L. B.; Lai, Y. Q.; Ji, X. B.; Yan, C. L. et al. Engineering Fe-N coordination structures for fast redox conversion in lithium-sulfur batteries. Adv. Mater. 2021, 33, 2100171.
Zhu, H.; Sun, S. H.; Hao, J. C.; Zhuang, Z. C.; Zhang, S. G.; Kang, Q. D.; Kang, Q.; Lu, S. L.; Wang, X. F.; Lai, F. L. et al. A high-entropy atomic environment converts inactive to active sites for electrocatalysis. Energy Environ. Sci. 2023, 16, 619–628.
Ma, F.; Wan, Y. Y.; Wang, X. M.; Wang, X. C.; Liang, J. S.; Miao, Z. P.; Wang, T. Y.; Ma, C.; Lu, G.; Han, J. T. et al. Bifunctional atomically dispersed Mo-N2/C nanosheets boost lithium sulfide deposition/decomposition for stable lithium-sulfur batteries. ACS Nano 2020, 14, 10115–10126.
Liu, Z. H.; Du, Y.; Yu, R. H.; Zheng, M. B.; Hu, R.; Wu, J. S.; Xia, Y. Y.; Zhuang, Z. C.; Wang, D. S. Tuning mass transport in electrocatalysis down to sub-5 nm through nanoscale grade separation. Angew. Chem., Int. Ed. 2023, 62, e202212653.
Wu, K. L.; Zhan, F.; Tu, R. Y.; Cheong, W. C.; Cheng, Y. S.; Zheng, L. R.; Yan, W. S.; Zhang, Q. H.; Chen, Z.; Chen, C. Dopamine polymer derived isolated single-atom site metals/N-doped porous carbon for benzene oxidation. Chem. Commun. 2020, 56, 8916–8919.
Liu, Z. H.; Du, Y.; Zhang, P. F.; Zhuang, Z. C.; Wang, D. S. Bringing catalytic order out of chaos with nitrogen-doped ordered mesoporous carbon. Matter 2021, 4, 3161–3194.
Dilpazir, S.; He, H. Y.; Li, Z. H.; Wang, M.; Lu, P. L.; Liu, R. J.; Xie, Z. J.; Gao, D. L.; Zhang, G. J. Cobalt single atoms immobilized N-doped carbon nanotubes for enhanced bifunctional catalysis toward oxygen reduction and oxygen evolution reactions. ACS Appl. Energy Mater. 2018, 1, 3283–3291.
Guo, D. Y.; Zhang, X.; Liu, M. L.; Yu, Z. S.; Chen, X. A.; Yang, B.; Zhou, Z.; Wang, S. Single Mo-N4 atomic sites anchored on N-doped carbon nanoflowers as sulfur host with multiple immobilization and catalytic effects for high-performance lithium-sulfur batteries. Adv. Funct. Mater. 2022, 32, 2204458.
Li, W. H.; Ye, B. C.; Yang, J. R.; Wang, Y.; Yang, C. J.; Pan, Y. M.; Tang, H. T.; Wang, D. S.; Li, Y. D. A single-atom cobalt catalyst for the fluorination of acyl chlorides at parts-per-million catalyst loading. Angew. Chem., Int. Ed. 2022, 61, e202209749.
Sun, T. T.; Zhao, S.; Chen, W. X.; Zhai, D.; Dong, J. C.; Wang, Y.; Zhang, S. L.; Han, A. J.; Gu, L.; Yu, R. et al. Single-atomic cobalt sites embedded in hierarchically ordered porous nitrogen-doped carbon as a superior bifunctional electrocatalyst. Proc. Nat. Acad. Sci. USA 2018, 115, 12692–12697.
Pan, Y.; Li, R.; Chen, Y. J.; Liu, S. J.; Zhu, W.; Cao, X.; Chen, W. X.; Wu, K. L.; Cheong, W. C.; Wang, Y. et al. Design of single-atom Co-N5 catalytic site: A robust electrocatalyst for CO2 reduction with nearly 100% CO selectivity and remarkable stability. J. Am. Chem. Soc. 2018, 140, 4218–4221.
Huang, X.; Wang, Z. L.; Knibbe, R.; Luo, B.; Ahad, S. A.; Sun, D.; Wang, L. Z. Cyclic voltammetry in lithium-sulfur batteries-challenges and opportunities. Energy Technol. 2019, 7, 1801001.
Geng, C. N.; Hua, W. X.; Wang, D. W.; Ling, G. W.; Zhang, C.; Yang, Q. H. Demystifying the catalysis in lithium-sulfur batteries: Characterization methods and techniques. SusMat 2021, 1, 51–65.
Zhuang, Z. C.; Li, Y.; Li, Y. H.; Huang, J. Z.; Wei, B.; Sun, B.; Ren, Y. J.; Ding, J.; Zhu, J. X.; Lang, Z. Q. et al. Atomically dispersed nonmagnetic electron traps improve oxygen reduction activity of perovskite oxides. Energy Environ. Sci. 2021, 14, 1016–1028.
Wang, H.; Adams, B. D.; Pan, H. L.; Zhang, L.; Han, K. S.; Estevez, L.; Lu, D. P.; Jia, H. P.; Feng, J.; Guo, J. H. et al. Tailored reaction route by micropore confinement for Li-S batteries operating under lean electrolyte conditions. Adv. Energy Mater. 2018, 8, 1800590.
Shen, C.; Xie, J. X.; Zhang, M.; Andrei, P.; Zheng, J. P.; Hendrickson, M.; Plichta, E. J. A Li-Li2S4 battery with improved discharge capacity and cycle life at low electrolyte/sulfur ratios. J. Power Sources 2019, 414, 412–419.
Zhan, Y.; Buffa, A.; Yu, L. H.; Xu, Z. J.; Mandler, D. Electrodeposited sulfur and CoxS electrocatalyst on buckypaper as high-performance cathode for Li-S batteries. Nano-Micro Lett. 2020, 12, 141.
Qian, J.; Wang, F. J.; Li, Y.; Wang, S.; Zhao, Y. Y.; Li, W. L.; Xing, Y.; Deng, L.; Sun, Q.; Li, L. et al. Electrocatalytic interlayer with fast lithium-polysulfides diffusion for lithium-sulfur batteries to enhance electrochemical kinetics under lean electrolyte conditions. Adv. Funct. Mater. 2020, 30, 2000742.
Xu, J.; Zhang, W. X.; Fan, H. B.; Cheng, F. L.; Su, D. W.; Wang, G. X. Promoting lithium polysulfide/sulfide redox kinetics by the catalyzing of zinc sulfide for high performance lithium-sulfur battery. Nano Energy 2018, 51, 73–82.
Yang, J. L.; Cai, D. Q.; Lin, Q. W.; Wang, X. Y.; Fang, Z. Q.; Huang, L.; Wang, Z. J.; Hao, X. G.; Zhao, S. X.; Li, J. et al. Regulating the Li2S deposition by grain boundaries in metal nitrides for stable lithium-sulfur batteries. Nano Energy 2022, 91, 106669.
Cañas, N. A.; Wolf, S.; Wagner, N.; Friedrich, K. A. In-situ X-ray diffraction studies of lithium-sulfur batteries. J. Power Sources 2013, 226, 313–319.
Hou, W. S.; Feng, P. L.; Guo, X.; Wang, Z. H.; Bai, Z.; Bai, Y.; Wang, G. X.; Sun, K. N. Catalytic mechanism of oxygen vacancies in perovskite oxides for lithium-sulfur batteries. Adv. Mater. 2022, 34, 2202222.
Weng, W.; Xiao, J. X.; Shen, Y. J.; Liang, X. X.; Lv, T.; Xiao, W. Molten salt electrochemical modulation of iron-carbon-nitrogen for lithium-sulfur batteries. Angew. Chem., Int. Ed. 2021, 60, 24905–24909.
Peng, L. L.; Wei, Z. Y.; Wan, C. Z.; Li, J.; Chen, Z.; Zhu, D.; Baumann, D.; Liu, H. T.; Allen, C. S.; Xu, X. et al. A fundamental look at electrocatalytic sulfur reduction reaction. Nat. Catal. 2020, 3, 762–770.
Zeng, Z. H.; Nong, W.; Li, Y.; Wang, C. X. Universal-descriptors-guided design of single atom catalysts toward oxidation of Li2S in lithium-sulfur batteries. Adv. Sci. 2021, 8, 2102809.
Zhou, G. M.; Tian, H. Z.; Jin, Y.; Tao, X. Y.; Liu, B. F.; Zhang, R. F.; Seh, Z. W.; Zhuo, D.; Liu, Y. Y.; Sun, J. et al. Catalytic oxidation of Li2S on the surface of metal sulfides for Li-S batteries. Proc. Natl. Acad. Sci. USA 2017, 114, 840–845.
Wang, R. R.; Wu, R. B.; Yan, X. X.; Liu, D.; Guo, P. F.; Li, W.; Pan, H. G. Implanting single Zn atoms coupled with metallic Co nanoparticles into porous carbon nanosheets grafted with carbon nanotubes for high-performance lithium-sulfur batteries. Adv. Funct. Mater. 2022, 32, 2200424.
Li, Y. J.; Wu, J. B.; Zhang, B.; Wang, W. Y.; Zhang, G. Q.; Seh, Z. W.; Zhang, N.; Sun, J.; Huang, L.; Jiang, J. J. et al. Fast conversion and controlled deposition of lithium (poly)sulfides in lithium-sulfur batteries using high-loading cobalt single atoms. Energy Storage Mater. 2020, 30, 250–259.
Zhou, X.; Meng, R. J.; Zhong, N.; Yin, S. F.; Ma, G. Q.; Liang, X. Size-dependent cobalt catalyst for lithium sulfur batteries: From single atoms to nanoclusters and nanoparticles. Small Methods 2021, 5, 2100571.
Zhang, S. L.; Ao, X.; Huang, J.; Wei, B.; Zhai, Y. L.; Zhai, D.; Deng, W. Q.; Su, C. L.; Wang, D. S.; Li, Y. D. Isolated single-atom Ni-N5 catalytic site in hollow porous carbon capsules for efficient lithium-sulfur batteries. Nano Lett. 2021, 21, 9691–9698.
Wang, J. Y.; Qiu, W. B.; Li, G. R.; Liu, J. B.; Luo, D.; Zhang, Y. G.; Zhao, Y.; Zhou, G. F.; Shui, L. L.; Wang, X. et al. Coordinatively deficient single-atom Fe-N-C electrocatalyst with optimized electronic structure for high-performance lithium-sulfur batteries. Energy Storage Mater. 2022, 46, 269–277.
Kim, J.; Kim, S. J.; Jung, E.; Mok, D. H.; Paidi, V. K.; Lee, J.; Lee, H. S.; Jeoun, Y.; Ko, W.; Shin, H. et al. Atomic structure modification of Fe-N-C catalysts via morphology engineering of graphene for enhanced conversion kinetics of lithium-sulfur batteries. Adv. Funct. Mater. 2022, 32, 2110857.
Fan, X. Y.; Chen, S.; Gong, W. B.; Meng, X. D.; Jia, Y. C.; Wang, Y. L.; Hong, S.; Zheng, L.; Zheng, L. R.; Bielawski, C. W. et al. A conjugated porous polymer complexed with a single-atom cobalt catalyst as an electrocatalytic sulfur host for enhancing cathode reaction kinetics. Energy Storage Mater. 2021, 41, 14–23.
Li, Y. J.; Chen, G. L.; Mou, J. R.; Liu, Y. Z.; Xue, S. F.; Tan, T.; Zhong, W. T.; Deng, Q.; Li, T.; Hu, J. H. et al. Cobalt single atoms supported on N-doped carbon as an active and resilient sulfur host for lithium-sulfur batteries. Energy Storage Mater. 2020, 28, 196–204.
Zhang, Y. G.; Liu, J. B.; Wang, J. Y.; Zhao, Y.; Luo, D.; Yu, A. P.; Wang, X.; Chen, Z. W. Engineering oversaturated Fe-N5 multifunctional catalytic sites for durable lithium-sulfur batteries. Angew. Chem., Int. Ed. 2021, 60, 26622–26629.
Chen, C. Y.; Peng, H. J.; Hou, T. Z.; Zhai, P. Y.; Li, B. Q.; Tang, C.; Zhu, W. C.; Huang, J. Q.; Zhang, Q. A quinonoid-imine-enriched nanostructured polymer mediator for lithium-sulfur batteries. Adv. Mater. 2017, 29, 1606802.
Cai, W. L.; Li, G. R.; Zhang, K. L.; Xiao, G. N.; Wang, C.; Ye, K. F.; Chen, Z. W.; Zhu, Y. C.; Qian, Y. T. Conductive nanocrystalline niobium carbide as high-efficiency polysulfides tamer for lithium-sulfur batteries. Adv. Funct. Mater. 2018, 28, 1704865.
Zhang, S. Z.; Zhong, N.; Zhou, X.; Zhang, M. J.; Huang, X. P.; Yang, X. L.; Meng, R. J.; Liang, X. Comprehensive design of the high-sulfur-loading Li-S battery based on MXene nanosheets. Nano-Micro Lett. 2020, 12, 112.
Lv, X. X.; Lei, T. Y.; Wang, B. J.; Chen, W.; Jiao, Y.; Hu, Y.; Yan, Y. C.; Huang, J. W.; Chu, J. W.; Yan, C. Y. et al. An efficient separator with low Li-ion diffusion energy barrier resolving feeble conductivity for practical lithium-sulfur batteries. Adv. Energy Mater. 2019, 9, 1901800.
Zhang, L. L.; Chen, X.; Wan, F.; Niu, Z. Q.; Wang, Y. J.; Zhang, Q.; Chen, J. Enhanced electrochemical kinetics and polysulfide traps of indium nitride for highly stable lithium-sulfur batteries. ACS Nano 2018, 12, 9578–9586.
Jiang, S. F.; Huang, S.; Yao, M. J.; Zhu, J. C.; Liu, L. L.; Niu, Z. Q. Bimetal-organic frameworks derived Co/N-doped carbons for lithium-sulfur batteries. Chin. Chem. Lett. 2020, 31, 2347–2352.
Tian, Y.; Li, G. R.; Zhang, Y. G.; Luo, D.; Wang, X.; Zhao, Y.; Liu, H.; Ji, P. G.; Du, X. H.; Li, J. D. et al. Low-bandgap Se-deficient antimony selenide as a multifunctional polysulfide barrier toward high-performance lithium-sulfur batteries. Adv. Mater. 2020, 32, 1904876.
Jin, H. G.; Wang, M. Y.; Wen, J. X.; Han, S. H.; Hong, X. J.; Cai, Y. P.; Li, G. L.; Fan, J. C.; Chao, Z. S. Oxygen vacancy-rich mixed-valence cerium MOF: An efficient separator coating to high-performance lithium-sulfur batteries. ACS Appl. Mater. Interfaces 2021, 13, 3899–3910.