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Trapping and catalytic conversion of polysulfides by kirkendall effect built hollow NiCo2S4 nano-prisms for advanced sulfur cathodes in Li–S battery

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Abstract

To address the problems of low active utilization and fast capacity decay in practical application of lithium–sulfur (Li–S) battery, an effective and widely used strategy is incorporating polar materials into sulfur cathode to tune the redox reaction of polysulfides in recent years. Herein, a hollow nano-prism structured bimetallic sulfide (NiCo2S4) built by kirkendall effect is proposed to trap and catalyze conversion of polysulfides. Beneficial from the strong interaction and super electrocatalytic effect for the intermediates of sulfur reduction, the NiCo2S4 incorporated in sulfur cathode can significantly ease the shuttle effect, decrease the activation energy and dynamically accelerates the transformation of the polysulfides. As expected, together with the high conductivity, hollow structure and compositional superiorities, the sulfur cathode with NiCo2S4 for Li–S battery exhibits apparently enhanced sulfur utilization and improved cycling performance that preserves super low capacity fading rate of 0.05% per cycle after 800 cycles at 1 C. This work has guiding significance in the design of a sulfur cathode for advanced Li–S battery.

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References

  1. Bhargav A, He JR, Gupta A, Manthiram A (2020) Lithium–sulfur batteries: attaining the critical metrics. Joule 4:285–291

    Google Scholar 

  2. Manthiram A, Chung SH, Zu C (2015) Lithium–sulfur batteries: progress and prospects. Adv Mater 27:1980–2006

    CAS  Google Scholar 

  3. Manthiram A, Fu Y, Chung SH, Zu C, Su YS (2014) Rechargeable lithium–sulfur batteries. Chem Rev 114:11751–11787

    CAS  Google Scholar 

  4. Bruce PG, Freunberger SA, Hardwick LJ, Tarascon JM (2011) Li–O2 and Li–S batteries with high energy storage. Nat Mater 11:19–29

    Google Scholar 

  5. Liu B, Fang RY, Xie D, Zhang WK, Huang H, Xia Y, Wang XL, Xia XH, Tu J (2018) Revisiting scientific issues for industrial applications of lithium–sulfur batteries. Energy Environ Mater 1:196–208

    Google Scholar 

  6. Bresser D, Passerini S, Scrosati B (2013) Recent progress and remaining challenges in sulfur-based lithium secondary batteries: a review. Chem Commun 49:10545–10562

    CAS  Google Scholar 

  7. Peng HJ, Huang JQ, Cheng XB, Zhang Q (2017) Review on high-loading and high-energy lithium–sulfur batteries. Adv Energy Mater 7:1700260

    Google Scholar 

  8. Pang Q, Liang X, Kwok CY, Nazar LF (2016) Advances in lithium–sulfur batteries based on multifunctional cathodes and electrolytes. Nat Energy 1:16132

    CAS  Google Scholar 

  9. Ge R, Lu M, Xu R, Zhang Z (2015) Graphene-based nano-materials for lithium-sulfur battery and sodium-ion battery. Nano Energy 15:379–405

    Google Scholar 

  10. Lin L, PeiPeng FJ, Fu A, Cui JQ, FangZheng XLNF (2018) Fiber network composed of interconnected yolk-shell carbon nanospheres for high-performance lithium–sulfur batteries. Nano Energy 54:50–58

    CAS  Google Scholar 

  11. Peng HJ, Xu WT, Zhu L, Wang DW, Huang JQ, Cheng XB, Yuan Z, Wei F, Zhang Q (2016) 3D Carbonaceous current collectors: the origin of enhanced cycling stability for high-sulfur-loading lithiums–sulfur batteries. Adv Funct Mater 26:6351–6358

    CAS  Google Scholar 

  12. Quan P, Kundu D, Nazar LF (2016) A graphene-like metallic cathode host for long-life and high-loading lithium–sulfur batteries. Mater Horiz 3:130–136

    Google Scholar 

  13. Rehman S, Gu X, Khan K, Mahmood N, Yang W, Huang X, Guo S, Hou Y (2016) 3D vertically aligned and interconnected porous carbon nanosheets as sulfur immobilizers for high performance lithium–sulfur batteries. Adv Energy Mater 6:1502518

    Google Scholar 

  14. Shi H, Wei L, Chen Z, Wang DW, Ling G, He Y, Kang F, Yang QH (2018) Functional carbons remedy the shuttling of polysulfides in lithium-sulfur batteries: confining, trapping, blocking, and breaking up. Adv Funct Mater 28:1800508

    Google Scholar 

  15. Ji XL, Lee KT, Nazar LF (2009) A highly ordered nanostructured carbon-sulphur cathode for lithium–sulphur batteries. Nat Mater 8:500–506

    CAS  Google Scholar 

  16. Yang Y, Zheng G, Cui Y (2013) Nanostructured sulfur cathodes. Chem Soc Rev 42:3018

    CAS  Google Scholar 

  17. Liu GX, Feng K, Cui HT, Li J, Liu YY, Wang MR (2020) MOF derived in-situ carbon-encapsulated Fe3O4@C to mediate polysulfides redox for ultrastable lithium–sulfur batteries. Chem Eng J 381:122652

    CAS  Google Scholar 

  18. Shi S, Sun C, Yin X, Shen L, Shi Q, Zhao K, Zhao Y, Zhang J (2020) FeP quantum dots confined in carbon-nanotube-grafted P-doped carbon octahedra for high-rate sodium storage and full-cell applications. Adv Funct Mater 30:1909283

    CAS  Google Scholar 

  19. Wang M, Liu G, Wang H, Zhang H, Li X, Zhang H (2018) Anchor and activate sulfide with LiTi2(PO4)2,88F0,12 nano spheres for lithium sulfur battery application. J Mater Chem A 6:7639–7648

    CAS  Google Scholar 

  20. Liu X, Huang JQ, Zhang Q, Mai L (2017) Nanostructured metal oxides and sulfides for lithium–sulfur batteries. Adv Mater 29:1601759

    Google Scholar 

  21. Yang H, Lin Q, Zhang C, Yu X, Cheng Z, Li G, Hu Q, Ren X, Zhang Q, Liu J, He C (2020) Carbon dioxide electro reduction on single-atom nickel decorated carbon membranes with industry compatible current densities. Nat Commun 11:593

    CAS  Google Scholar 

  22. Ye H, Sun J, Zhang S, Lin H, Zhang T, Yao Q, Lee JY (2019) Stepwise electrocatalysis as a strategy against polysulfide shuttling in Li–S batteries. ACS Nano 13:14208–14216

    CAS  Google Scholar 

  23. Yu QH, Lu Y, Luo RJ, Liu XM, Huo KF, Kim JK, He J, Luo Y (2018) In situ formation of copper-based hosts embedded within 3D N-Doped hierarchically porous carbon networks for ultralong cycle lithium–sulfur batteries. Adv Funct Mater 28:1804520

    Google Scholar 

  24. Zhang Q, Li F, Huang JQ, Li H (2018) Lithium–sulfur batteries: Co-existence of challenges and opportunities. Adv Funct Mater 28:1804589

    Google Scholar 

  25. Zhang ZW, Peng HJ, Zhao M, Huang JQ (2018) Heterogeneous/homogeneous mediators for high-energy-density lithium–sulfur batteries: progress and prospects. Adv Funct Mater 28:1707536

    Google Scholar 

  26. Zhong Y, Yin L, He P, Liu W, Wu Z, Wang H (2018) Surface chemistry in cobalt phosphide-stabilized lithium–sulfur batteries. J Am Chem Soc 140:1455–1459

    CAS  Google Scholar 

  27. Yang XF, GaoXJ SQ, Jand SP, Yu Y, Zhao Y, Li X, Adair K, Kuo LY, Rohrer J, Liang JN, Lin XT, Banis MN, Hu YF, Zhang HZ, Li XF, Li RY, Zhang HM, Kaghazchi P, Sham T-K, Sun XL (2019) Promoting the Transformation of Li2S2–Li2S: significantly increasing utilization of active materials for high-sulfur-loading Li–S Batteries. Adv Mater 31:1901220

    Google Scholar 

  28. Jia ZY, Zhang HZ, Yu Y, Chen YQ, Yan JW, Li XF, Zhang HM (2020) Trithiocyanuric acid derived g-C3N4 for anchoring the polysulfide in Li–S batteries application. J Energy Chem 43:71–77

    Google Scholar 

  29. Li S, Xu P, Aslam MK, Chen CG, Rashid A, Wang GL, Zhang L, Mao BW (2020) Propelling polysulfide conversion for high-loading lithium-sulfur batteries through highly sulfiphilic NiCo2S4 nanotubes. Energy Storage Mater 27:51–60

    Google Scholar 

  30. Dai CL, Hu LY, Li XY, Xu QJ, Wang R, Liu H, Chen H, Bao SJ, Chen YM, Henkelman G, Li CM, Xu MW (2018) Chinese knot-like electrode design for advanced Li–S batteries. Nano Energy 53:354–361

    CAS  Google Scholar 

  31. Wang C, Wang H, Hu X, Matios E, Luo J, Zhang Y, Lu X, Li W (2018) Frogspawn-coral-like hollow sodium sulfide nanostructured cathode for high-rate performance sodium-sulfur batteries. Adv Energy Mater 1803251. https://doi.org/10.1002/aenm.201803251

    Article  Google Scholar 

  32. Yuan Z, Peng HJ, Hou TZ, Huang JQ, Chen CM, Wang DW, Cheng XB, Wei F, Zhang Q (2016) Powering lithium–sulfur battery performance by propelling polysulfide redox at sulfiphilic hosts. Nano Lett 16:519–527

    CAS  Google Scholar 

  33. Zhang J, Li Z, Lou XW (2017) A freestanding selenium disulfide cathode based on cobalt disulfide-decorated multichannel carbon fibers with enhanced lithium storage performance. Angew Chem Int Ed Engl 56:14107–14112

    CAS  Google Scholar 

  34. Feng J, Yin Y (2019) Self-templating approaches to hollow nanostructures. Adv Mater 31:1802349

    Google Scholar 

  35. Gai YS, Xie T, Shang YY, Su LH, Wang J, Gong LY (2020) Self-sacrificing template-derived hollow-structured NiCo2S4 spheres with highly efficient supercapacitance performance. Energy Fuel 34:10203–10210

    CAS  Google Scholar 

  36. Wang ZN, Wang H, Ji S, Wang XY, Zhou PX, Huo SH, Linkov V, Wang RF (2020) Hollow-structured NiCoP nanorods as high-performance electrodes for asymmetric supercapacitors. Mater Des 193:108807

    CAS  Google Scholar 

  37. Yu L, Zhang L, Wu HB, Lou XW (2014a) Formation of NixCo3-xS4 hollow nanoprisms with enhanced pseudocapacitive properties. Angew Chem Int Ed Engl 126:3785–3788

    Google Scholar 

  38. Zhou G, Zhao Y, Manthiram A (2015) Dual-confined flexible sulfur cathodes encapsulated in nitrogen-doped double-shelled hollow carbon spheres and wrapped with graphene for Li–S batteries. Adv Energy Mater 5:1402263

    Google Scholar 

  39. Yu L, Zhang L, Wu HB, Lou XW (2014b) Formation of Ni(x)Co(3–x)S(4) hollow nanoprisms with enhanced pseudocapacitive properties. Angew Chem Int Ed Engl 53:3711–3714

    CAS  Google Scholar 

  40. Liu GX, Zhang HY, Li J, Liu YY, Wang MR (2019) Ultrathin nanosheets-assembled NiCo2S4 nanocages derived from ZIF-67 for high-performance supercapacitors. J Mater Sci 54:9666–9678. https://doi.org/10.1016/j.cej.2019.122210

    Article  CAS  Google Scholar 

  41. Peng HJ, Zhang G, Chen X, Zhang ZW, Xu WT, Huang JQ, Zhang Q (2016) Enhanced electrochemical kinetics on conductive polar mediators for lithium–sulfur batteries. Angew Chem Int Ed Engl 55:12990–12995

    CAS  Google Scholar 

  42. Hwang JY, Kim HM, Lee SK, Lee JH, Abouimrane A, Khaleel MA, Belharouak I, Manthiram A, Sun YK (2016) High-energy, high-rate, lithium-sulfur batteries: synergetic effect of hollow tio2-webbed carbon nanotubes and a dual functional carbon-paper interlayer. Adv Energy Mater 6:1670001

    Google Scholar 

  43. Kong L, Li BQ, Peng HJ, Zhang R, Xie J, Huang JQ, Zhang Q (2018) Porphyrin-derived graphene-based nanosheets enabling strong polysulfide chemisorption and rapid kinetics in lithium–sulfur batteries. Adv Energy Mater 8:1800849

    Google Scholar 

  44. Lim WG, Kim S, Jo C, Lee J (2019) A comprehensive review of materials with catalytic effects in Li–S batteries: enhanced redox kinetics. Angew Chem Int Ed Engl 58:18746–18757

    CAS  Google Scholar 

  45. Li Z, Zhang JT, Chen YM, Li J, Lou XW (2015) Pie-like electrode design for high-energy density lithium-sulfur batteries. Nat Commun 6:8850

    CAS  Google Scholar 

  46. Meng J, He Q, Xu L, Zhang X, Liu F, Wang X, Li Q, Xu X, Zhang G, Niu C (2019) Identification of phase control of carbon-confined Nb2O5 nanoparticles toward high-performance lithium storage. Adv Energy Mater 9:1802695

    Google Scholar 

  47. Chung SH, Manthiram A (2018) Rational design of statically and dynamically stable lithium-sulfur batteries with high sulfur loading and low electrolyte/sulfur ratio. Adv Mater 30:1705951

    Google Scholar 

  48. Wang M, Zhang H, Zhou W, Yang X, Li X, Zhang H (2016) Rational design of a nested pore structure sulfur host for fast Li/S batteries with a long cycle life. J Mater Chem A 4:1653–1662

    CAS  Google Scholar 

  49. Zhou JW, Li R, Fan XX, Chen YF, Han RD, Li W, Zheng J, Wang B, Li X (2014) Rational design of a metal-organic framework host for sulfur storage in fast, long-cycle Li–S batteries. Energy Environ Sci 7:2715–2729

    CAS  Google Scholar 

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Acknowledgements

The authors acknowledge Key Research and Development Program of Shandong Province (2019GGX103006), Yantai Science and Technology Project (2019XDHZ088), Natural Science Foundation of Shandong Province (No. ZR2019MEM036), and Major scientific and technological innovation project of Shandong Province (No. 2019JZZY010908).

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  1. Shandong Collaborative Innovation Center of Light Hydrocarbon Transformation and Utilization, School of Chemistry and Chemical Engineering, Yantai University, Yantai, 264005, China

    Huaiyue Zhang, Guanxi Liu, Jing Li, Hongtao Cui, Yuanyuan Liu & Meiri Wang

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Zhang, H., Liu, G., Li, J. et al. Trapping and catalytic conversion of polysulfides by kirkendall effect built hollow NiCo2S4 nano-prisms for advanced sulfur cathodes in Li–S battery. J Mater Sci 56, 4328–4340 (2021). https://doi.org/10.1007/s10853-020-05511-8

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