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Functional separator for Li/S batteries based on boron-doped graphene and activated carbon

  • Baoe Li
  • Zhenghao Sun
  • Yan ZhaoEmail author
  • Yuan Tian
  • Taizhe Tan
  • Fan Gao
  • Jingde LiEmail author
Research Paper
  • 57 Downloads

Abstract

Lithium/sulfur (Li/S) batteries have received great attention due to their high theoretical energy density, but the “shuttle effect” of polysulfides restricts the further development of Li/S batteries. The construction of modified functional separator is an effective strategy to obstruct the diffusion of polysulfides. We report boron-doped graphene and activated carbon (B-G/AC)–modified functional separator for Li/S batteries. The B-G/AC composites are obtained via a one-step hydrothermal method and used as a functional layer to modify the battery separator. The B-G with highly porous three-dimensional (3D) network structure exhibits good electrical conductivity, and rich porous structure AC increases the specific surface area of the B-G/AC composite. The carbon coating layer can act as the second collector, utilizing the inactivated sulfur that is freed in the electrolyte. The modified separator can facilitate the polysulfide dissolution and migration towards the anode. The B-G/AC samples exhibit excellent electrochemical performances. The B-G/AC samples maintain a higher capacity of 1062 mA h g−1 after 100 cycles at 0.1 C than a routine separator (709 mA h g−1 after 100 cycles at 0.1 C). Diffusion experiments of polysulfides in U-shaped bottles also proved importance of B-G/AC as a separator. In addition, the B-G/AC samples also exhibit excellent cycling stability over 300 cycles, delivering a discharge capacity of 534 mA h g−1 when the current is 1 C. The present study confirms that separator modification is an effective technique that leads to good electrochemical performance.

Graphical abstract

Long-term cyclic performance of Li/S batteries with different separators at 1 C and photograph of polysulfide diffusion process across with B-G/AC separator.

Keywords

Li/S batteries Boron-doped graphene/activated carbon (B-G/AC) Electrochemical performance Shuttle effect Functional separator Energy storage 

Notes

Funding information

This study received support from the Natural Science Foundation of Hebei Province of China (Project No. E2017202032) and Technology Foundation for returned overseas Chinese scholars (No. C2015003038).

Compliance with ethical standards

All relevant ethical standards were satisfied.

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11051_2018_4451_MOESM1_ESM.doc (1.2 mb)
ESM 1 (DOC 1204 kb)

References

  1. Chai LY, Wang JX, Wang HY, Zhang LY, Yu WT, Mai LQ (2015) Porous carbonized graphene-embedded fungus film as an interlayer for superior Li-S batteries. Nano Energy 17:224–232CrossRefGoogle Scholar
  2. Chong L, Chen P, Huang J, Huang H (2018) Capacitive deionization of a RO brackish water by AC/graphene composite electrodes. Chemosphere 191:296–301CrossRefGoogle Scholar
  3. Chowdhury S, Jiang Y, Muthukaruppan S, Balasubramanian R (2018) Effect of boron doping level on the photocatalytic activity of graphene aerogels. Carbon 128:237–248CrossRefGoogle Scholar
  4. Ganesana A, Varzib A, Passerini S, Shaijumona M (2016) Graphene derived carbon confined sulfur cathodes for lithium-sulfur batteries: electrochemical impedance studies. Electrochim Acta 214:129–138CrossRefGoogle Scholar
  5. Gao SH, Ren ZY, Wan LJ, Zheng JM, Guo P, Zhou YX (2011) Density functional theory prediction for diffusion of lithium on boron-doped graphene surface. Appl Surf Sci 257:7443–7446CrossRefGoogle Scholar
  6. Gnedenkov SV, Sinebryukhov SL, Zheleznov VV, Opra DP, Voit EI, Modin EB, Sokolov AA, Ustinov AU, Sergienko VI (2018) Effect of Hf-doping on electrochemical performance of anatase TiO2 as an anode material for lithium storage. R Soc Open Sci 5:171811CrossRefGoogle Scholar
  7. Han P, Manthiram A (2017) Boron- and nitrogen-doped reduced graphene oxide separators for high-performance Li-S batteries. J Power Sources 369:87–94CrossRefGoogle Scholar
  8. He X, Shuai Y, Na L, Chen KH, Zhang YG, Zhang ZP, Gan FY (2018) High performance lithium-sulfur batteries with facile titanium nitride particles modified separator. Mater Lett 215:91–94CrossRefGoogle Scholar
  9. Huang JQ, Zhang Q, Wei F (2015) Multi-functional separator/interlayer system for high-stable lithium-sulfur batteries: progress and prospects. Energy Storage Mater 1:127–145CrossRefGoogle Scholar
  10. Hummers WS, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339CrossRefGoogle Scholar
  11. Kang J, Atashin S, Jayaram S, Wen JZ (2017) Frequency and temperature dependent electrochemical characteristics of carbon-based electrodes made of commercialized activated carbon, graphene and single-walled carbon nanotube. Carbon 111:338–349CrossRefGoogle Scholar
  12. Kong WB, Wang DT, Yan LJ, Luo YF, Jiang KL, Li QQ, Zhang L, Lu SG, Fan SS, Li J, Wang JP (2018) Ultrathin HfO2-modified carbon nanotube films as efficient polysulfide barriers for Li-S batteries. Carbon 139:896–905CrossRefGoogle Scholar
  13. Lee SK, Lee YJ, Sun YK (2016) Nanostructured lithium sulfide materials for lithium-sulfur batteries. J Power Sources 323:174–188CrossRefGoogle Scholar
  14. Lee DH, Ahn JW, Park MS, Eftekhari A, Kim DW (2018) Metal-organic framework/carbon nanotube-coated polyethylene separator for improving the cycling performance of lithium-sulfur cells. Electrochim Acta 283:1291–1299CrossRefGoogle Scholar
  15. Li CX, Dong SH, Guo DX, Zhang ZW, Wang MQ, Yin LW (2017a) Ternary NiO/RGO-Sn hybrid flexible freestanding film as interlayer for lithium-sulfur batteries with improved performance. Electrochim Acta 251:43–50CrossRefGoogle Scholar
  16. Li HP, Sun LC, Zhang YG, Tan TZ, Wang GK, Bakenov Z (2017b) Enhanced cycle performance of Li/S battery with the reduced graphene oxide/activated carbon functional interlayer. J Energy Chem 26:1276–1281CrossRefGoogle Scholar
  17. Li HP, Sun LC, Wang Z, Zhang YG, TZ T, GK W, Bakenov Z (2018) Three-dimensionally hierarchical graphene based aerogel encapsulated sulfur as cathode for lithium/sulfur batteries. Nanomaterials 8:69CrossRefGoogle Scholar
  18. Li HP, Sun LC, Zhao Y, Tan TZ, Y Zhang YG (2019) A novel CuS/graphene-coated separator for suppressing the shuttle effect of lithium/sulfur batteries. Appl Surf Sci 466:309–319CrossRefGoogle Scholar
  19. Ma GQ, Wen ZY, Jin J, Wu MF, Wu XW, Zhang JC (2014) Enhanced cycle performance of Li-S battery with a polypyrrole functional interlayer. J Power Sources 267:542–546CrossRefGoogle Scholar
  20. Opra DP, Gnedenkov SV, Sinebryukhov SL, Voit EI, Sokolov AA, Modin EB, Podgorbunsky AB, Sushkov YV, Zheleznov VV (2017) Characterization and electrochemical properties of nanostructured Zr-doped anatase TiO2 tubes synthesized by sol-gel template route. J Mater Sci Technol 33:527–534CrossRefGoogle Scholar
  21. Opra DP, Gnedenkov SV, Sinebryukhov SL, Voit EI, Sokolov AA, Ustinov AY, Zheleznov VV (2018) Zr4+/F co-doped TiO2 (anatase) as high performance anode material for lithium-ion battery. Prog Nat Sci 28:542–547CrossRefGoogle Scholar
  22. Pei F, Lin LL, Fu A, Mo SG, Ou DH, Fang XL, Zheng NF (2018) A two-dimensional porous carbon-modified separator for high-energy-density Li-S batteries. Joule 2:323–336CrossRefGoogle Scholar
  23. Sahoo M, Sreena K, Vinayan B, Ramaprabhu S (2015) Green synthesis of boron doped graphene and its application as high-performance anode material in Li ion battery. Mater Res Bull 61:383–390CrossRefGoogle Scholar
  24. Shao HY, Wang WK, Zhang H, Wang AB, Chen XN, Huang YQ (2018) Nano-TiO2 decorated carbon coating on the separator to physically and chemically suppress the shuttle effect for lithium-sulfur battery. J Power Sources 378:537–545CrossRefGoogle Scholar
  25. Strubel P, Thieme S, Weller C, Althues H, Kaskel S (2017) Insights into the redistribution of sulfur species during cycling in lithium-sulfur batteries using physisorption methods. Nano Energy 34:437–441CrossRefGoogle Scholar
  26. Tang H, Yao SS, Xue SK, Liu MQ, Chen LL, Jing MX, Shen XQ, Li TB, Xiao KS, Qin SB (2018) In-situ synthesis of carbon@Ti4O7 non-woven fabric as a multifunctional interlayer for excellent lithium-sulfur battery. Electrochim Acta 263:158–167CrossRefGoogle Scholar
  27. Wu F, Shi LL, Mu DB, Xu HL, Wu BR (2015) A hierarchical carbon fiber/sulfur composite as cathode material for Li-S batteries. Carbon 86:146–155CrossRefGoogle Scholar
  28. Wu X, Fan LS, Qiu Y, Wang MX, Cheng JH, Guan B, Guo ZK, Zhang NQ, Sun KN (2018) Ionic selectivity Prussian blue modified Celgard separator for high performance lithium sulfur battery. ChemSusChem 11:3345–3351CrossRefGoogle Scholar
  29. Yan LJ, Luo N, Kong WB, Luo S, Wu HC, Jiang KL, Li Q, Fan SS, Duan WH, Wang JP (2018) Enhanced performance of lithium-sulfur batteries with an ultrathin and lightweight MoS2/carbon nanotube interlayer. J Power Sources 389:169–177CrossRefGoogle Scholar
  30. Yang W, Yang W, Feng JN, Ma ZP, Shao GJ (2016) High capacity and cycle stability rechargeable lithium-sulfur batteries by sandwiched gel polymer electrolyte. Electrochim Acta 210:71–78CrossRefGoogle Scholar
  31. Yu XM, Han P, Wei ZX, Peng SJ, Ma JM, Zheng GF (2018) Boron-doped graphene for electrocatalytic N2 reduction. Joule 2:1610–1622CrossRefGoogle Scholar
  32. Zhang K, Li Q, Zhang LY, Fang J, Li J, Qin FR, Zhang Z, Lai YQ (2014a) From filter paper to carbon paper and toward Li-S battery interlayer. Mater Lett 121:198–201CrossRefGoogle Scholar
  33. Zhang YG, Zhao Y, Bakenov Z, Konarov A, Chen P (2014b) Preparation of novel network nanostructured sulfur composite cathode with enhanced stable cycle performance. J Power Sources 270:326–331CrossRefGoogle Scholar
  34. Zhang YG, Zhao Y, Konarov A, Li Z, Chen P (2015a) Effect of mesoporous carbon microtube prepared by carbonizing the poplar catkin on sulfur cathode performance in Li/S batteries. J Alloys Compd 619:298–302CrossRefGoogle Scholar
  35. Zhang ZY, Lai YQ, Zhang ZA, Li J (2015b) A functional carbon layer-coated separator for high performance lithium sulfur batteries. Solid State Ionics 278:166–171CrossRefGoogle Scholar
  36. Zhang X, Xie H, Kim C, Zaghib K, Mauger A, Julien CM (2017) Advances in lithium-sulfur batteries. Mater Sci Eng R 121:1–29CrossRefGoogle Scholar
  37. Zhang YG, Sun LC, Li HP, Tan TZ, Li JD (2018) Porous three-dimensional reduced graphene oxide for high performance lithium-sulfur batteries. J Alloys Compd 739:290–297CrossRefGoogle Scholar
  38. Zhou XY, Liao QC, Tang JJ, Bai T, Chen F, Yang J (2016) A high-level N-doped porous carbon nanowire modified separator for long-life lithium-sulfur batteries. J Electroanal Chem 768:55–61CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2018

Authors and Affiliations

  1. 1.School of Materials Science and EngineeringHebei University of TechnologyTianjinChina
  2. 2.Synergy Innovation Institute of GDUTHeyuanChina
  3. 3.School of Chemical EngineeringHebei University of TechnologyTianjinChina

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