Issue

Vol. 12 (2020)

Sandwiching Sulfur into the Dents Between N, O Co-Doped Graphene Layered Blocks with Strong Physicochemical Confinements for Stable and High-Rate Li–S Batteries

https://doi.org/10.1007/s40820-020-00477-3
Mengjiao Shi
Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, People’s Republic of China
Su Zhang
Key Laboratory of Energy Materials Chemistry, Ministry of Education, Key Laboratory of Advanced Functional Materials, Autonomous Region, Institute of Applied Chemistry, Xinjiang University, Urumqi 830046, People’s Republic of China
Yuting Jiang
Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, People’s Republic of China
Zimu Jiang
Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, People’s Republic of China
Longhai Zhang
Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, People’s Republic of China
Jin Chang
Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, People’s Republic of China
Tong Wei
Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, People’s Republic of China
Zhuangjun Fan
Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, People’s Republic of China

Corresponding Author: Zhuangjun Fan

fanzhj666@163.com

Nano-Micro Letters, Vol. 12 (2020), Article Number: 146

Abstract

The development of lithium–sulfur batteries (LSBs) is restricted by their poor cycle stability and rate performance due to the low conductivity of sulfur and severe shuttle effect. Herein, an N, O co-doped graphene layered block (NOGB) with many dents on the graphene sheets is designed as effective sulfur host for high-performance LSBs. The sulfur platelets are physically confined into the dents and closely contacted with the graphene scaffold, ensuring structural stability and high conductivity. The highly doped N and O atoms can prevent the shuttle effect of sulfur species by strong chemical adsorption. Moreover, the micropores on the graphene sheets enable fast Li+ transport through the blocks. As a result, the obtained NOGB/S composite with 76 wt% sulfur content shows a high capacity of 1413 mAh g−1 at 0.1 C, good rate performance of 433 mAh g−1 at 10 C, and remarkable stability with 526 mAh g−1 at after 1000 cycles at 1 C (average decay rate: 0.038% per cycle). Our design provides a comprehensive route for simultaneously improving the conductivity, ion transport kinetics, and preventing the shuttle effect in LSBs.


Highlights:


1 N, O co-doped graphene layered block (NOGB) was prepared as sulfur host for lithium–sulfur batteries.
2 The NOGB/S shows good rate performance due to robust electrochemical kinetics.
3 The strong physicochemical confinement leads to an improved cycling stability.

Keywords

Graphene Physicochemical confinement Cycle stability Shuttle effect Li–S batteries
Shi, Mengjiao, Su Zhang, Yuting Jiang, Zimu Jiang, Longhai Zhang, Jin Chang, Tong Wei, and Zhuangjun Fan. 2020. “Sandwiching Sulfur into the Dents Between N, O Co-Doped Graphene Layered Blocks With Strong Physicochemical Confinements for Stable and High-Rate Li–S Batteries”. Nano-Micro Letters 12 (July):146. https://doi.org/10.1007/s40820-020-00477-3.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. X. Ji, L.F. Nazar, Advances in Li–S batteries. J. Mater. Chem. 20(44), 9821–9826 (2010). https://doi.org/10.1039/b925751a
  2. M. Jana, R. Xu, X.-B. Cheng, J.S. Yeon, J.M. Park, J.-Q. Huang, Q. Zhang, H.S. Park, Rational design of two-dimensional nanomaterials for lithium–sulfur batteries. Energy Environ. Sci. (2019). https://doi.org/10.1039/c9ee02049g
  3. G. Li, S. Wang, Y. Zhang, M. Li, Z. Chen, J. Lu, Revisiting the role of polysulfides in lithium–sulfur batteries. Adv. Mater. 30(22), e1705590 (2018). https://doi.org/10.1002/adma.201705590
  4. Z. Chen, J. Chen, F. Bu, P.O. Agboola, I. Shakir, Y. Xu, Double-holey-heterostructure frameworks enable fast, stable and simultaneous ultrahigh gravimetric, areal, and volumetric lithium storage. ACS Nano 12, 12879–12887 (2018). https://doi.org/10.1021/acsnano.8b08071
  5. F. Liu, Q. Xiao, H.B. Wu, F. Sun, X. Liu et al., Regenerative polysulfide-scavenging layers enabling lithium-sulfur batteries with high energy density and prolonged cycling life. ACS Nano 11(3), 2697–2705 (2017). https://doi.org/10.1021/acsnano.6b07603
  6. Q. Li, Y. Song, R. Xu, L. Zhang, J. Gao et al., Biotemplating growth of nepenthes-like N-doped graphene as a bifunctional polysulfide scavenger for Li–S batteries. ACS Nano 12(10), 10240–10250 (2018). https://doi.org/10.1021/acsnano.8b05246
  7. Y. Pang, J.S. Wei, Y.G. Wang, Y.Y. Xia, Synergetic protective effect of the ultralight MWCNTs/NCQDs modified separator for highly stable lithium–sulfur batteries. Adv. Energy Mater. 8(10), 1702288 (2018). https://doi.org/10.1002/aenm.201702288
  8. Y.F. Yang, J.P. Zhang, Highly stable lithium–sulfur batteries based on laponite nanosheet-coated celgard separators. Adv. Energy Mater. 8(25), 1801778 (2018). https://doi.org/10.1002/aenm.201801778
  9. M. Liu, Q. Li, X. Qin, G. Liang, W. Han et al., Suppressing self-discharge and shuttle effect of lithium–sulfur batteries with V2O5-decorated carbon nanofiber interlayer. Small 13(12), 1602539 (2017). https://doi.org/10.1002/smll.201602539
  10. H. Pan, K.S. Han, M.H. Engelhard, R. Cao, J. Chen et al., Lean electrolyte batteries: addressing passivation in lithium-sulfur battery under lean electrolyte condition. Adv. Funct. Mater. 28(38), 1870275 (2018). https://doi.org/10.1002/adfm.201870275
  11. H. Xu, S. Wang, A. Manthiram, Hybrid lithium–sulfur batteries with an advanced gel cathode and stabilized lithium-metal anode. Adv. Energy Mater. (2018). https://doi.org/10.1002/aenm.201800813
  12. S.S. Zhang, Role of LiNO3 in rechargeable lithium/sulfur battery. Electrochim. Acta 70, 344–348 (2012). https://doi.org/10.1016/j.electacta.2012.03.081
  13. M. Agostini, D.H. Lim, M. Sadd, J.Y. Hwang, S. Brutti et al., Rational design of low cost and high energy lithium batteries through tailored fluorine-free electrolyte and nanostructured S/C composite. Chemsuschem 11(17), 2981–2986 (2018). https://doi.org/10.1002/cssc.201801017
  14. H. Shi, W. Lv, C. Zhang, D.-W. Wang, G. Ling, Y. He, F. Kang, Q.-H. Yang, Functional carbons remedy the shuttling of polysulfides in lithium–sulfur batteries: confining, trapping, blocking, and breaking up. Adv. Funct. Mater. (2018). https://doi.org/10.1002/adfm.201800508
  15. Z. Zeng, X. Liu, Sulfur immobilization by “chemical anchor” to suppress the diffusion of polysulfides in lithium–sulfur batteries. Adv. Mater. Interfaces 5(4), 1701274 (2018). https://doi.org/10.1002/admi.201701274
  16. MathSciNet
  17. J. Lee, J. Oh, Y. Jeon, Y. Piao, Multi-heteroatom-doped hollow carbon attached on graphene using LiFePO4 nanoparticles as hard templates for high-performance lithium–sulfur batteries. ACS Appl. Mater. Interfaces. 10(31), 26485–26493 (2018). https://doi.org/10.1021/acsami.8b00925
  18. X. Ma, G. Ning, Y. Wang, X. Song, Z. Xiao, L. Hou, W. Yang, J. Gao, Y. Li, S-doped mesoporous graphene microspheres: a high performance reservoir material for Li–S batteries. Electrochim. Acta 269, 83–92 (2018). https://doi.org/10.1016/j.electacta.2018.02.163
  19. H. Tang, J. Yang, G. Zhang, C. Liu, H. Wang, Q. Zhao, J. Hu, Y. Duan, F. Pan, Self-assembled N-graphene nanohollows enabling ultrahigh energy density cathode for Li–S batteries. Nanoscale 10(1), 386–395 (2017). https://doi.org/10.1039/c7nr06731c
  20. P. Wu, L.H. Chen, S.S. Xiao, S. Yu, Z. Wang, Y. Li, B.L. Su, Insight into the positive effect of porous hierarchy in S/C cathodes on the electrochemical performance of Li–S batteries. Nanoscale 10(25), 11861–11868 (2018). https://doi.org/10.1039/c8nr03290d
  21. H. Wu, L. Xia, J. Ren, Q. Zheng, C. Xu, D. Lin, A high-efficiency N/P co-doped graphene/CNT@porous carbon hybrid matrix as a cathode host for high performance lithium–sulfur batteries. J. Mater. Chem. A 5(38), 20458–20472 (2017). https://doi.org/10.1039/c7ta06504c
  22. X.-Q. Zhang, B. He, W.-C. Li, A.-H. Lu, Hollow carbon nanofibers with dynamic adjustable pore sizes and closed ends as hosts for high-rate lithium–sulfur battery cathodes. Nano Res. 11(3), 1238–1246 (2018). https://doi.org/10.1007/s12274-017-1737-6
  23. G. Li, W. Lei, D. Luo, Y. Deng, Z. Deng, D. Wang, A. Yu, Z. Chen, Stringed “tube on cube” nanohybrids as compact cathode matrix for high-loading and lean-electrolyte lithium–sulfur batteries. Energy Environ. Sci. 11, 2372–2381 (2018). https://doi.org/10.1039/c8ee01377b
  24. H. Zhang, Q. Gao, W. Qian, H. Xiao, Z. Li, L. Ma, X. Tian, Binary hierarchical porous graphene/pyrolytic carbon nanocomposite matrix loaded with sulfur as a high-performance Li–S battery cathode. ACS Appl. Mater. Interfaces. 10(22), 18726–18733 (2018). https://doi.org/10.1021/acsami.8b03806
  25. P. Shi, Y. Wang, X. Liang, Y. Sun, S. Cheng, C. Chen, H. Xiang, Simultaneously exfoliated boron-doped graphene sheets to encapsulate sulfur for applications in lithium–sulfur batteries. ACS Sustain. Chem. Eng. 6(8), 9661–9670 (2018). https://doi.org/10.1021/acssuschemeng.8b00378
  26. S. Liu, J. Li, X. Yan, Q. Su, Y. Lu et al., Superhierarchical cobalt-embedded nitrogen-doped porous carbon nanosheets as two-in-one hosts for high-performance lithium–sulfur batteries. Adv. Mater. 30(12), e1706895 (2018). https://doi.org/10.1002/adma.201706895
  27. H.-E. Wang, X. Li, N. Qin, X. Zhao, H. Cheng, G. Cao, W. Zhang, Sulfur-deficient MoS2 grown inside hollow mesoporous carbon as a functional polysulfide mediator. J. Mater. Chem. A 7(19), 12068–12074 (2019). https://doi.org/10.1039/c9ta01722d
  28. J. He, G. Hartmann, M. Lee, G.S. Hwang, Y. Chen, A. Manthiram, Freestanding 1T MoS2/graphene heterostructures as a highly efficient electrocatalyst for lithium polysulfides in Li–S batteries. Energy Environ. Sci. 12(1), 344–350 (2019). https://doi.org/10.1039/c8ee03252a
  29. L. Meng, Y. Yao, J. Liu, Z. Wang, D. Qian, L. Zheng, B.-L. Su, H.-E. Wang, MoSe2 nanosheets as a functional host for lithium–sulfur batteries. J. Energy Chem. 47, 241–247 (2020). https://doi.org/10.1016/j.jechem.2020.02.003
  30. W. Dong, D. Wang, X. Li, Y. Yao, X. Zhao et al., Bronze TiO2 as a cathode host for lithium–sulfur batteries. J. Energy Chem. 48, 259–266 (2020). https://doi.org/10.1016/j.jechem.2020.01.022
  31. H.-E. Wang, K. Yin, N. Qin, X. Zhao, F.-J. Xia et al., Oxygen-deficient titanium dioxide as a functional host for lithium–sulfur batteries. J. Mater. Chem. A 7(17), 10346–10353 (2019). https://doi.org/10.1039/c9ta01598a
  32. Y. Wang, R. Zhang, J. Chen, H. Wu, S. Lu et al., Enhancing catalytic activity of titanium oxide in lithium–sulfur batteries by band engineering. Adv. Energy Mater. 9(24), 1900953 (2019). https://doi.org/10.1002/aenm.201900953
  33. G. Yuan, H. Jin, Y. Jin, L. Wu, Hybrids of MnO2 nanoparticles anchored on graphene sheets as efficient sulfur hosts for high-performance lithium sulfur batteries. J. Solid State Electrochem. 22(3), 693–703 (2017). https://doi.org/10.1007/s10008-017-3799-5
  34. Y. Zhang, X. Liu, L. Wu, W. Dong, F. Xia et al., A flexible, hierarchically porous PANI/MnO2 network with fast channels and an extraordinary chemical process for stable fast-charging lithium–sulfur batteries. J. Mater. Chem. A 8(5), 2741–2751 (2020). https://doi.org/10.1039/c9ta12135h
  35. T.Z. Hou, X. Chen, H.J. Peng, J.Q. Huang, B.Q. Li, Q. Zhang, B. Li, Design principles for heteroatom-doped nanocarbon to achieve strong anchoring of polysulfides for lithium–sulfur batteries. Small 12(24), 3283–3291 (2016). https://doi.org/10.1002/smll.201600809
  36. H. Yang, X. Zhang, W. Zhu, F. Wang, Y. Li, Q. Fan, H. Xiao, F. Zhang, Graphene oxide induced growth of nitrogen-doped carbon nanotubes as a 1D/2D composite for high-performance lithium–sulfur batteries. ChemElectroChem 6(4), 1115–1121 (2019). https://doi.org/10.1002/celc.201801445
  37. M. Zhang, C. Yu, J. Yang, C. Zhao, Z. Ling, J. Qiu, Nitrogen-doped tubular/porous carbon channels implanted on graphene frameworks for multiple confinement of sulfur and polysulfides. J. Mater. Chem. A 5(21), 10380–10386 (2017). https://doi.org/10.1039/c7ta01512g
  38. F. Pei, T. An, J. Zang, X. Zhao, X. Fang, M. Zheng, Q. Dong, N. Zheng, From hollow carbon spheres to N-doped hollow porous carbon bowls: rational design of hollow carbon host for Li–S batteries. Adv. Energy Mater. 6(8), 1502539 (2016). https://doi.org/10.1002/aenm.201502539
  39. L. Sheng, L. Jiang, T. Wei, Z. Fan, High volumetric energy density asymmetric supercapacitors based on well-balanced graphene and graphene–MnO2 electrodes with densely stacked architectures. Small 12(37), 5217–5227 (2016). https://doi.org/10.1002/smll.201601722
  40. Q.H. Zhou, J. Chang, Y.T. Jiang, T. Wei, L.Z. Sheng, Z.J. Fan, Fast charge rate supercapacitors based on nitrogen-doped aligned carbon nanosheet networks. Electrochim. Acta 251, 91–98 (2017). https://doi.org/10.1016/j.electacta.2017.08.106
  41. L.H. Zhang, J.M. Yue, T. Wei, Z. Liu, J.L. Zhou et al., Densely pillared holey-graphene block with high-level nitrogen doping enabling ultra-high volumetric capacity for lithium ion storage. Carbon 142, 327–336 (2019). https://doi.org/10.1016/j.carbon.2018.10.070
  42. J. Wang, X. Yan, Z. Zhang, H. Ying, R. Guo, W. Yang, W.Q. Han, Facile preparation of high-content N-doped CNT microspheres for high-performance lithium storage. Adv. Funct. Mater. 29(39), 1904819 (2019). https://doi.org/10.1002/adfm.201904819
  43. N. Wang, Z. Xu, X. Xu, T. Liao, B. Tang, Z. Bai, S. Dou, Synergistically enhanced interfacial interaction to polysulfide via N, O dual-doped highly porous carbon microrods for advanced lithium–sulfur batteries. ACS Appl. Mater. Interfaces. 10(16), 13573–13580 (2018). https://doi.org/10.1021/acsami.8b02084
  44. S.-K. Park, J.-K. Lee, Y.C. Kang, Yolk-shell structured assembly of bamboo-like nitrogen-doped carbon nanotubes embedded with Co nanocrystals and their application as cathode material for Li–S batteries. Adv. Funct. Mater. 28(18), 1705264 (2018). https://doi.org/10.1002/adfm.201705264
  45. X. Zhu, W. Zhao, Y. Song, Q. Li, F. Ding, J. Sun, L. Zhang, Z. Liu, In situ assembly of 2D conductive vanadium disulfide with graphene as a high-sulfur-loading host for lithium–sulfur batteries. Adv. Energy Mater. (2018). https://doi.org/10.1002/aenm.201800201
  46. J. Zhang, J.-Y. Li, W.-P. Wang, X.-H. Zhang, X.-H. Tan, W.-G. Chu, Y.-G. Guo, Microemulsion assisted assembly of 3D porous S/graphene@g-C3N4 hybrid sponge as free-standing cathodes for high energy density Li–S batteries. Adv. Energy Mater. 8(14), 1702839 (2018). https://doi.org/10.1002/aenm.201702839
  47. W. Ren, L. Xu, L. Zhu, X. Wang, X. Ma, D. Wang, Cobalt-doped vanadium nitride yolk-shell nanospheres @ carbon with physical and chemical synergistic effect for advanced Li–S batteries. ACS Appl. Mater. Interfaces. 10(14), 11642–11651 (2018). https://doi.org/10.1021/acsami.7b18955
  48. X. Zhou, J. Tian, Q. Wu, J. Hu, C. Li, N/O dual-doped hollow carbon microspheres constructed by holey nanosheet shells as large-grain cathode host for high loading Li–S batteries. Energy Storage Mater. 24, 644–654 (2020). https://doi.org/10.1016/j.ensm.2019.06.009
  49. Y. Wang, R. Zhang, Y.-C. Pang, X. Chen, J. Lang et al., Carbon@titanium nitride dual shell nanospheres as multi-functional hosts for lithium sulfur batteries. Energy Storage Mater. 16, 228–235 (2019). https://doi.org/10.1016/j.ensm.2018.05.019
  50. Z.X. Cao, R.R. Zhang, M.J. Shi, G.S. Zhu, M.G. Yang, H.S. Zhang, Y. Qiao, S.T. Yang, Rational design oxygen and sulfur dual-doped 3D hierarchical porous carbons for high-performance lithium–sulfur batteries. J. Electrochem. Soc. 165(2), A31–A39 (2018). https://doi.org/10.1149/2.0041802jes
  51. J.-Q. Huang, W.G. Chong, Q. Zheng, Z.-L. Xu, J. Cui, S. Yao, C. Wang, J.-K. Kim, Understanding the roles of activated porous carbon nanotubes as sulfur support and separator coating for lithium–sulfur batteries. Electrochim. Acta 268, 1–9 (2018). https://doi.org/10.1016/j.electacta.2018.02.096
  52. Q. Liu, J. Zhang, S.A. He, R. Zou, C. Xu et al., Stabilizing lithium-sulfur batteries through control of sulfur aggregation and polysulfide dissolution. Small (2018). https://doi.org/10.1002/smll.201703816
  53. H. Wu, L. Xia, J. Ren, Q. Zheng, F. Xie, W. Jie, C. Xu, D. Lin, A multidimensional and nitrogen-doped graphene/hierarchical porous carbon as a sulfur scaffold for high performance lithium sulfur batteries. Electrochim. Acta 278, 83–92 (2018). https://doi.org/10.1016/j.electacta.2018.05.032
  54. H. Xu, A. Manthiram, Hollow cobalt sulfide polyhedra-enabled long-life, high areal-capacity lithium–sulfur batteries. Nano Energy 33, 124–129 (2017). https://doi.org/10.1016/j.nanoen.2017.01.007
  55. F. Sun, H. Tang, B. Zhang, X. Li, C. Yin et al., PEO-linked MoS2–graphene nanocomposites with 2D polar–nonpolar amphoteric surfaces as sulfur hosts for high-performance Li–S batteries. ACS Sustainable Chem. Eng. 6(1), 974–982 (2017). https://doi.org/10.1021/acssuschemeng.7b03306
  56. Y. Zhang, J. Ren, Y. Zhao, T. Tan, F. Yin, Y. Wang, A porous 3D-rGO@MWCNT hybrid material as Li–S battery cathode. Beilstein J Nanotechnol. 10, 514–521 (2019). https://doi.org/10.3762/bjnano.10.52
  57. J. Li, C. Xue, B. Xi, H. Mao, Y. Qian, S. Xiong, Heteroatom dopings and hierarchical pores of graphene for synergistic improvement of lithium–sulfur battery performance. Inorg. Chem. Front. 5(5), 1053–1061 (2018). https://doi.org/10.1039/c8qi00160j
  58. F. Li, G. Hu, S. Li, C. Hou, J. Gao, Dual-confined sulfur cathodes based on SnO2-decorated MoS2 microboxes for long-life lithium–sulfur batteries. Electrochim. Acta 340, 135991 (2020). https://doi.org/10.1016/j.electacta.2020.135991
  59. T. Chen, Z. Zhang, B. Cheng, R. Chen, Y. Hu, L. Ma, G. Zhu, J. Liu, Z. Jin, Self-templated formation of interlaced carbon nanotubes threaded hollow Co3S4 nanoboxes for high-rate and heat-resistant lithium–sulfur batteries. J. Am. Chem. Soc. 139(36), 12710–12715 (2017). https://doi.org/10.1021/jacs.7b06973
  60. L. Lai, J.R. Potts, D. Zhan, L. Wang, C.K. Poh et al., Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction. Energy Environ. Sci. 5(7), 7936 (2012). https://doi.org/10.1039/c2ee21802j
  61. J. Zhang, M. Huang, B. Xi, K. Mi, A. Yuan, S. Xiong, Systematic study of effect on enhancing specific capacity and electrochemical behaviors of lithium–sulfur batteries. Adv. Energy Mater. 8(2), 1701330 (2018). https://doi.org/10.1002/aenm.201701330
  62. D. Cheng, Y. Zhao, X. Tang, T. An, X. Wang, H. Zhou, D. Zhang, T. Fan, Densely integrated Co, N-codoped graphene @ carbon nanotube porous hybrids for high-performance lithium–sulfur batteries. Carbon 149, 750–759 (2019). https://doi.org/10.1016/j.carbon.2019.04.108
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY MATERIAL
Statistic
Read Counter : 5047 Download : 3814

Most read articles by the same author(s)