Skip to main content
Log in

The strategies of advanced cathode composites for lithium-sulfur batteries

  • Review
  • Published:
Science China Technological Sciences Aims and scope Submit manuscript

Abstract

Lithium-sulfur batteries have been widely nominated as one of the most promising next-generation electrochemical storage systems due to its low cost, high capacity and energy density. However, its practical application is still hindered by poor cycling lifetime, low Coulombic efficiency, instability and small scales. In the last decade, the electrochemical performances of the lithium-sulfur batteries have been improved by developing various novel nanoarchitectures as qualified hosts, and enhancing the sulfur loading with effective encapsulating strategies. The review summarizes the major sulfur cooperating strategies of cathodes based on background and latest progress of the lithium-sulfur batteries. The novel cooperating strategies of physical techniques and chemical synthesis techniques are discussed in detail. Based on the rich chemistry of sulfur, we paid more attention to the highlights of sulfur encapsulating strategies. Furthermore, the critical research directions in the coming future are proposed in the conclusion and outlook section.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Bruce P G, Freunberger S A, Hardwick L J, et al. Li-O2 and Li-S batteries with high energy storage. Nat Mater, 2012, 11: 19–29

    Article  Google Scholar 

  2. Zhang Y, Li Y, Xia X, et al. High-energy cathode materials for Li-ion batteries: A review of recent developments. Sci China Tech Sci, 2015, 58: 1809–1828

    Article  Google Scholar 

  3. Yang M, Xia H. Exploration and progress of high-energy supercapacitors and related electrode materials. Sci China Tech Sci, 2015, 58: 1851–1863

    Article  Google Scholar 

  4. Yin Y X, Xin S, Guo Y G, et al. Lithium-sulfur batteries: Electrochemistry, materials, and prospects. Angew Chem Int Ed, 2013, 52: 13186–13200

    Article  Google Scholar 

  5. Xu R, Belharouak I, Zhang X, et al. Insight into sulfur reactions in Li-S batteries. ACS Appl Mater Interfaces, 2014, 6: 21938–21945

    Article  Google Scholar 

  6. Manthiram A, Fu Y, Chung S H, et al. Rechargeable lithium-sulfur batteries. Chem Rev, 2014, 114: 11751–11787

    Article  Google Scholar 

  7. Guo J, Xu Y, Wang C. Sulfur-impregnated disordered carbon nanotubes cathode for lithium-sulfur batteries. Nano Lett, 2011, 11: 4288–4294

    Article  Google Scholar 

  8. Schuster J, He G, Mandlmeier B, et al. Spherical ordered mesoporous carbon nanoparticles with high porosity for lithium-sulfur batteries. Angew Chem Int Ed, 2012, 124: 3651–3655

    Article  Google Scholar 

  9. Zhou W, Xiao X, Cai M, et al. Polydopamine-coated, nitrogen-doped, hollow carbon-sulfur double-layered core-shell structure for improving lithium-sulfur batteries. Nano Lett, 2014, 14: 5250–5256

    Article  Google Scholar 

  10. Elazari R, Salitra G, Garsuch A, et al. Sulfur-impregnated activated carbon fiber cloth as a binder-free cathode for rechargeable Li-S batteries. Adv Mater, 2011, 23: 5641–5644

    Article  Google Scholar 

  11. Zhang B, Qin X, Li G, et al. Enhancement of long stability of sulfur cathode by encapsulating sulfur into micropores of carbon spheres. Energy Environ Sci, 2010, 3: 1531–1537

    Article  Google Scholar 

  12. Ji L, Rao M, Zheng H, et al. Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells. J Am Chem Soc, 2011, 133: 18522–18525

    Article  Google Scholar 

  13. Pang Q, Kundu D, Cuisinier M, et al. Surface-enhanced redox chemistry of polysulphides on a metallic and polar host for lithium-sulphur batteries. Nat Commun, 2014, 5: 4759

    Article  Google Scholar 

  14. Liang X, Nazar L F. In situ reactive assembly of scalable core-shell sulfur-MnO2 composite cathodes. ACS Nano, 2016, 10: 4192–4198

    Article  Google Scholar 

  15. Yuan Z, Peng H J, Hou T Z, et al. Powering lithium-sulfur battery performance by propelling polysulfide redox at sulfiphilic hosts. Nano Lett, 2016, 16: 519–527

    Article  Google Scholar 

  16. Pang Q, Nazar L F. Long-life and high-areal-capacity Li-S batteries enabled by a light-weight polar host with intrinsic polysulfide adsorption. ACS Nano, 2016, 10: 4111–4118

    Article  Google Scholar 

  17. Song J, Xu T, Gordin M L, et al. Nitrogen-doped mesoporous carbon promoted chemical adsorption of sulfur and fabrication of high-areal-capacity sulfur cathode with exceptional cycling stability for lithium-sulfur batteries. Adv Funct Mater, 2014, 24: 1243–1250

    Article  Google Scholar 

  18. Pang Q, Tang J, Huang H, et al. A nitrogen and sulfur dual-doped carbon derived from polyrhodanine@cellulose for advanced lithium- sulfur batteries. Adv Mater, 2015, 27: 6021–6028

    Article  Google Scholar 

  19. Zhang J, Hu H, Li Z, et al. Double-shelled nanocages with cobalt hydroxide inner shell and layered double hydroxides outer shell as high-efficiency polysulfide mediator for lithium-sulfur batteries. Angew Chem Int Ed, 2016, 55: 3982–3986

    Article  Google Scholar 

  20. Song J, Gordin M L, Xu T, et al. 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

    Article  Google Scholar 

  21. Kang S H, Zhao X, Manuel J, et al. Effect of sulfur loading on energy density of lithium sulfur batteries. Phys Status Solidi A, 2014, 211: 1895–1899

    Article  Google Scholar 

  22. Cheon S E, Ko K S, Cho J H, et al. Rechargeable lithium sulfur battery ii. Rate capability and cycle characteristics. J Electrochem Soc, 2003, 150: A800–A805

    Google Scholar 

  23. Li G, Ling M, Ye Y, et al. Acacia senegal-inspired bifunctional binder for longevity of lithium-sulfur batteries. Adv Energy Mater, 2015, 5: 878–886

    Google Scholar 

  24. Zhang S S. Improved cyclability of liquid electrolyte lithium/sulfur batteries by optimizing electrolyte/sulfur ratio. Energies, 2012, 5: 5190–5197

    Article  Google Scholar 

  25. Wang J G, Xie K, Wei B. Advanced engineering of nanostructured carbons for lithium-sulfur batteries. Nano Energy, 2015, 15: 413–444

    Article  Google Scholar 

  26. Zhang S, Ueno K, Dokko K, et al. Recent advances in electrolytes for lithium-sulfur batteries. Adv Energy Mater, 2015, 5: 1500117

    Article  Google Scholar 

  27. Cao R, Xu W, Lv D, et al. Anodes for rechargeable lithium-sulfur batteries. Adv Energy Mater, 2015, 5: 1402273

    Article  Google Scholar 

  28. Urbonaite S, Poux T, Novák P. Progress towards commercially viable Li-S battery cells. Adv Energy Mater, 2015, 5: 1500118

    Article  Google Scholar 

  29. Liu M, Ye F, Li W, et al. Chemical routes toward long-lasting lithium/ sulfur cells. Nano Res, 2016, 9: 94–116

    Article  Google Scholar 

  30. Xu R, Lu J, Amine K. Progress in mechanistic understanding and characterization techniques of Li-S batteries. Adv Energy Mater, 2015, 5: 1500408

    Article  Google Scholar 

  31. Wild M, O’ Neill L, Zhang T, et al. Lithium sulfur batteries, a mechanistic review. Energy Environ Sci, 2015, 8: 3477–3494

    Article  Google Scholar 

  32. Pope M A, Aksay I A. Structural design of cathodes for Li-S batteries. Adv Energy Mater, 2015, 5: 1500124

    Article  Google Scholar 

  33. Choudhary T V, Malandra J, Green J, et al. Towards clean fuels: Molecular-level sulfur reactivity in heavy oils. Angew Chem Int Ed, 2006, 45: 3299–3303

    Article  Google Scholar 

  34. Yang R T, Hernández- Maldonado A J, Yang F H. Desulfurization of transportation fuels with zeolites under ambient conditions. Science, 2003, 301: 79–81

    Article  Google Scholar 

  35. Wang D W, Zeng Q, Zhou G, et al. Carbon-sulfur composites for Li-S batteries: Status and prospects. J Mater Chem A, 2013, 1: 9382–9394

    Article  Google Scholar 

  36. Song J, Yu Z, Gordin M L, et al. Advanced sodium ion battery anode constructed via chemical bonding between phosphorus, carbon nanotube, and cross-linked polymer binder. ACS Nano, 2015, 9: 11933–11941

    Article  Google Scholar 

  37. Song J, Yu Z, Gordin M L, et al. Chemically bonded phosphorus/ graphene hybrid as a high performance anode for sodium-ion batteries. Nano Lett, 2014, 14: 6329–6335

    Article  Google Scholar 

  38. Kim Y, Park Y, Choi A, et al. An amorphous red phosphorus/carbon composite as a promising anode material for sodium ion batteries. Adv Mater, 2013, 25: 3045–3049

    Article  Google Scholar 

  39. Lin T, Tang Y, Wang Y, et al. Scotch-tape-like exfoliation of graphite assisted with elemental sulfur and graphene-sulfur composites for high-performance lithium-sulfur batteries. Energy Environ Sci, 2013, 6: 1283–1290

    Article  Google Scholar 

  40. Xu J, Shui J, Wang J, et al. Sulfur-graphene nanostructured cathodes via ball-milling for high-performance lithium-sulfur batteries. ACS Nano, 2014, 8: 10920–10930

    Article  Google Scholar 

  41. Cai K, Song M K, Cairns E J, et al. Nanostructured Li2S-C composites as cathode material for high-energy lithium/sulfur batteries. Nano Lett, 2012, 12: 6474–6479

    Article  Google Scholar 

  42. Zhang J, Yang C P, Yin Y X, et al. Sulfur encapsulated in graphitic carbon nanocages for high-rate and long-cycle lithium-sulfur batteries. Adv Mater, 2016, in press, doi: 10.1002/adma.201602913

    Google Scholar 

  43. Sun L, Li M, Jiang Y, et al. Sulfur nanocrystals confined in carbon nanotube network as a binder-free electrode for high-performance lithium sulfur batteries. Nano Lett, 2014, 14: 4044–4049

    Article  Google Scholar 

  44. Sun L, Wang D, Luo Y, et al. Sulfur embedded in a mesoporous carbon nanotube network as a binder-free electrode for high-performance lithium-sulfur batteries. ACS Nano, 2015, 10: 1300–1308

    Article  Google Scholar 

  45. Sun L, Kong W, Jiang Y, et al. Super-aligned carbon nanotube/graphene hybrid materials as a framework for sulfur cathodes in high performance lithium sulfur batteries. J Mater Chem A, 2015, 3: 5305–5312

    Article  Google Scholar 

  46. Ji X, Lee K T, Nazar L F. A highly ordered nanostructured carbon- sulphur cathode for lithium-sulphur batteries. Nat Mater, 2009, 8: 500–506

    Article  Google Scholar 

  47. Li X, Cao Y, Qi W, et al. Optimization of mesoporous carbon structures for lithium-sulfur battery applications. J Mater Chem A, 2011, 21: 16603–16610

    Article  Google Scholar 

  48. Tang C, Li B Q, Zhang Q, et al. CaO-templated growth of hierarchical porous graphene for high-power lithium-sulfur battery applications. Adv Funct Mater, 2016, 26: 577–585

    Article  Google Scholar 

  49. Zhang C, Wu H B, Yuan C, et al. Confining sulfur in double-shelled hollow carbon spheres for lithium-sulfur batteries. Angew Chem Int Ed, 2012, 124: 9730–9733

    Article  Google Scholar 

  50. Liang Z, Zheng G, Li W, et al. Sulfur cathodes with hydrogen reduced titanium dioxide inverse opal structure. ACS Nano, 2014, 8: 5249–5256

    Article  Google Scholar 

  51. Pang Q, Kundu D, Nazar L F. A graphene-like metallic cathode host for long-life and high-loading lithium-sulfur batteries. Mater Horiz, 2016, 3: 130–136

    Article  Google Scholar 

  52. Meyer B. Elemental sulfur. Chem Rev, 1976, 76: 367–388

    Article  Google Scholar 

  53. Zheng S, Wen Y, Zhu Y, et al. In-situ sulfur reduction and intercalation of graphite oxides for Li-S battery cathodes. Adv Energy Mater, 2014, 4: 1400482

    Article  Google Scholar 

  54. Luo C, Zhu Y, Borodin O, et al. Activation of oxygen-stabilized sulfur for Li and Na batteries. Adv Funct Mater, 2016, 26: 745–752

    Article  Google Scholar 

  55. Zhang S S, Read J A. A new direction for the performance improvement of rechargeable lithium/sulfur batteries. J Power Sources, 2012, 200: 77–82

    Article  Google Scholar 

  56. Choi J W, Aurbach D. Promise and reality of post-lithium-ion batteries with high energy densities. Nat Rev Mater, 2016, 1: 16013

    Article  Google Scholar 

  57. Tang C, Zhang Q, Zhao M Q, et al. Nitrogen-doped aligned carbon nanotube/graphene sandwiches: Facile catalytic growth on bifunctional natural catalysts and their applications as scaffolds for highrate lithium-sulfur batteries. Adv Mater, 2014, 26: 6100–6105

    Article  Google Scholar 

  58. Zhou G, Pei S, Li L, et al. A graphene-pure-sulfur sandwich structure for ultrafast, long-life lithium-sulfur batteries. Adv Mater, 2014, 26: 625–631

    Article  Google Scholar 

  59. Zhou G, Li L, Wang D W, et al. A flexible sulfur-graph-enepolypropylene separator integrated electrode for advanced Li-S batteries. Adv Mater, 2015, 27: 641–647

    Article  Google Scholar 

  60. Qie L, Manthiram A. High-energy-density lithium-sulfur batteries based on blade-cast pure sulfur electrodes. ACS Energy Lett, 2016, 1: 46–51

    Article  Google Scholar 

  61. Wang H, Zhang W, Liu H, et al. A strategy for configuration of an integrated flexible sulfur cathode for high-performance lithium-sulfur batteries. Angew Chem Int Ed, 2016, 55: 3992–3996

    Article  Google Scholar 

  62. Zheng S, Yi F, Li Z, et al. Copper-stabilized sulfur-microporous carbon cathodes for Li-S batteries. Adv Funct Mater, 2014, 24: 4156–4163

    Article  Google Scholar 

  63. Zhou G, Yin L C, Wang D W, et al. Fibrous hybrid of graphene and sulfur nanocrystals for high-performance lithium-sulfur batteries. ACS Nano, 2013, 7: 5367–5375

    Article  Google Scholar 

  64. Xu J, Zhou K, Chen F, et al. Natural integrated carbon architecture for rechargeable lithium-sulfur batteries. ACS Sustain Chem Eng, 2016, 4: 666–670

    Article  Google Scholar 

  65. Chen H, Wang C, Dong W, et al. Monodispersed sulfur nanoparticles for lithium-sulfur batteries with theoretical performance. Nano Lett, 2015, 15: 798–802

    Article  Google Scholar 

  66. Zhang B, Lai C, Zhou Z, et al. Preparation and electrochemical properties of sulfur-acetylene black composites as cathode materials. Electrochim Acta, 2009, 54: 3708–3713

    Article  Google Scholar 

  67. Yang X, Zhang L, Zhang F, et al. Sulfur-infiltrated graphene-based layered porous carbon cathodes for high-performance lithium-sulfur batteries. ACS Nano, 2014, 8: 5208–5215

    Article  Google Scholar 

  68. Xu Y, Wen Y, Zhu Y, et al. Confined sulfur in microporous carbon renders superior cycling stability in Li-S batteries. Adv Funct Mater, 2015, 25: 4312–4320

    Article  Google Scholar 

  69. Liang X, Garsuch A, Nazar L F. Sulfur cathodes based on conductive MXene nanosheets for high-performance lithium-sulfur batteries. Angew Chem Int Ed, 2015, 54: 3907–3911

    Article  Google Scholar 

  70. Je S H, Hwang T H, Talapaneni S N, et al. A rational sulfur cathode design for lithium-sulfur batteries: Sulfur-embedded benzoxazine polymers. ACS Energy Lett, 2016, 1: 566–572

    Article  Google Scholar 

  71. Zhang C, Lv W, Zhang W, et al. Reduction of graphene oxide by hydrogen sulfide: A promising strategy for pollutant control and as an electrode for Li-S batteries. Adv Energy Mater, 2014, 4: 1301565

    Article  Google Scholar 

  72. He B, Li W C, Yang C, et al. Incorporating sulfur inside the pores of carbons for advanced lithium-sulfur batteries: An electrolysis approach. ACS Nano, 2016, 10: 1633–1639

    Article  Google Scholar 

  73. Zhou G, Wang D W, Li F, et al. A flexible nanostructured sulphur- carbon nanotube cathode with high rate performance for Li-S batteries. Energy Environ Sci, 2012, 5: 8901–8906

    Article  Google Scholar 

  74. Wang H, Yang Y, Liang Y, et al. Graphene-wrapped sulfur particles as a rechargeable lithium-sulfur battery cathode material with high capacity and cycling stability. Nano Lett, 2011, 11: 2644–2647

    Article  Google Scholar 

  75. Zhou W, Yu Y, Chen H, et al. Yolk-shell structure of polyaniline- coated sulfur for lithium-sulfur batteries. J Am Chem Soc, 2013, 135: 16736–16743

    Article  Google Scholar 

  76. Simmonds A G, Griebel J J, Park J, et al. Inverse vulcanization of elemental sulfur to prepare polymeric electrode materials for Li-S batteries. ACS Macro Lett, 2014, 3: 229–232

    Article  Google Scholar 

  77. Ding B, Chang Z, Xu G, et al. Nanospace-confinement copolymerization strategy for encapsulating polymeric sulfur into porous carbon for lithium-sulfur batteries. ACS Appl Mater Interfaces, 2015, 7: 11165–11171

    Article  Google Scholar 

  78. Kim H, Lee J, Ahn H, et al. Synthesis of three-dimensionally interconnected sulfur-rich polymers for cathode materials of high-rate lithium-sulfur batteries. Nat Commun, 2015, 6: 7278

    Article  Google Scholar 

  79. Talapaneni S N, Hwang T H, Je S H, et al. Elemental-sulfur-mediated facile synthesis of a covalent triazine framework for high-performance lithium-sulfur batteries. Angew Chem Int Ed, 2016, 128: 3158–3163

    Article  Google Scholar 

  80. Dirlam P T, Simmonds A G, Kleine T S, et al. Inverse vulcanization of elemental sulfur with 1, 4-diphenylbutadiyne for cathode materials in Li-S batteries. RSC Adv, 2015, 5: 24718–24722

    Article  Google Scholar 

  81. Li B, Li S, Xu J, et al. A new configured lithiated silicon-sulfur battery built on 3D graphene with superior electrochemical performances. Energy Environ Sci, 2016, 9: 2025–2030

    Article  Google Scholar 

  82. Fei L, Li X, Bi W, et al. Graphene/sulfur hybrid nanosheets from a space-confined “sauna” reaction for high-performance lithium-sulfur batteries. Adv Mater, 2015, 27: 5936–5942

    Article  Google Scholar 

  83. Ding N, Lum Y, Chen S, et al. Sulfur-carbon yolk-shell particle based 3D interconnected nanostructures as cathodes for rechargeable lithium-sulfur batteries. J Mater Chem A, 2015, 3: 1853–1857

    Article  Google Scholar 

  84. Li G, Sun J, Hou W, et al. Three-dimensional porous carbon composites containing high sulfur nanoparticle content for high-performance lithium-sulfur batteries. Nat Commun, 2016, 7: 10601

    Article  Google Scholar 

  85. Hernandez Y, Nicolosi V, Lotya M, et al. High-yield production of graphene by liquid-phase exfoliation of graphite. Nat Nanotechnol, 2008, 3: 563–568

    Article  Google Scholar 

  86. Liu Z, Ma R, Osada M, et al. Synthesis, anion exchange, and delamination of Co-Al layered double hydroxide: Assembly of the exfoliated nanosheet/polyanion composite films and magneto-optical studies. J Am Chem Soc, 2006, 128: 4872–4880

    Article  Google Scholar 

  87. Chung W J, Griebel J J, Kim E T, et al. The use of elemental sulfur as an alternative feedstock for polymeric materials. Nat Chem, 2013, 5: 518–524

    Article  Google Scholar 

  88. Naguib M, Kurtoglu M, Presser V, et al. Two-dimensional nanocrystals produced by exfoliation of Ti3AlC2. Adv Mater, 2011, 23: 4248–4253

    Article  Google Scholar 

  89. Naguib M, Mochalin V N, Barsoum M W, et al. MXenes: A new family of two-dimensional materials. Adv Mater, 2014, 26: 992–1005

    Article  Google Scholar 

  90. Naguib M, Gogotsi Y. Synthesis of two-dimensional materials by selective extraction. Acc Chem Res, 2014, 48: 128–135

    Article  Google Scholar 

  91. Zhao M Q, Sedran M, Ling Z, et al. Synthesis of carbon/sulfur nanolaminates by electrochemical extraction of titanium from Ti2SC. Angew Chem Int Ed, 2015, 54: 4810–4814

    Article  Google Scholar 

  92. Zhao Q, Hu X, Zhang K, et al. Sulfur nanodots electrodeposited on Ni foam as high-performance cathode for Li-S batteries. Nano Lett, 2015, 15: 721–726

    Article  Google Scholar 

  93. Li B, Li S, Liu J, et al. Vertically aligned sulfur-graphene nanowalls on substrates for ultrafast lithium-sulfur batteries. Nano Lett, 2015, 15: 3073–3079

    Article  Google Scholar 

  94. Huang C, Xiao J, Shao Y, et al. Manipulating surface reactions in lithium-sulphur batteries using hybrid anode structures. Nat Commun, 2014, 5: 3015

    Google Scholar 

  95. Huang J Q, Zhuang T Z, Zhang Q, et al. Permselective graphene oxide membrane for highly stable and anti-self-discharge lithium-sulfur batteries. ACS Nano, 2015, 9: 3002–3011

    Article  Google Scholar 

  96. Ma L, Zhuang H, Lu Y, et al. Tethered molecular sorbents: Enabling metal-sulfur battery cathodes. Adv Energy Mater, 2014, 4: 1400390

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to JieHua Liu.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhou, K., Fan, X., Wei, X. et al. The strategies of advanced cathode composites for lithium-sulfur batteries. Sci. China Technol. Sci. 60, 175–185 (2017). https://doi.org/10.1007/s11431-016-0664-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11431-016-0664-0

Keywords

Navigation