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Nano-silicon/polyaniline composites with an enhanced reversible capacity as anode materials for lithium ion batteries

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Abstract

Silicon nanoparticles are coated with the conductive polyaniline (PANI) using in situ polymerization method as anode materials to improve the electrochemical performance for lithium ion batteries. At first, the physicochemical and electrochemical properties of the doped polyaniline in the lithium ion electrolyte are investigated. After that, the effect of different contents of PANI for preparing Si/PANI composites on the composition and structure and thus the electrochemical performance are investigated. The structure and morphology of as-prepared materials are characterized systematically by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). It is demonstrated that the silicon/polyaniline composite presents the core/shell structure. The Si/PANI composite with 12.3 wt% PANI exhibits the optimum electrochemical performance. The electrode still maintains better reversible capacity of 766.6 mAh g−1, and the capacity retention of 72 % is retained after 50 cycles at current density of 2 A g−1. The good electrochemical properties can be attributed to the PANI-coating layer, which can improve the electrical conductivity of the Si-based anode materials for lithium ion batteries and accommodate the volume change of silicon during the charge-discharge processes.

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References

  1. Armand M, Tarascon JM (2008) Building better batteries. Nature 451:652–657

  2. Guo YG, Hu JS, Wan LJ (2008) Nanostructured materials for electrochemical energy conversion and storage devices. Adv Mater 20:2878–2887

  3. Hu YS, Demir-Cakan R, Titirici MM, Müller JO, Schlögl R, Antonietti M, Maier J (2008) Superior storage performance of a Si@SiOx/C nanocomposite as anode material for lithium-ion batteries. Angew Chem Int Ed 47:1645–1649

  4. Magasinski A, Zdyrko B, Kovalenko I, Hertzberg B, Burtovyy R, Huebner CF, Fuller TF, Luzinov I, Yushin G (2010) Toward efficient binders for Li-ion battery Si-based anodes: polyacrylic acid. ACS Appl Mater Interfaces 2:3004–3010

  5. Wu H, Zheng G, Liu N, Carney TJ, Yang Y, Cui Y (2012) Engineering empty space between Si nanoparticles for lithium-ion battery anodes. Nano Lett 12:904–909

  6. Zhao L, Han SH, Okada S, Na BK, Takeno K, Yamaki JI (2012) Thermal stability of silicon negative electrode for Li-ion batteries. J Power Sources 203:78–83

  7. Ryu JH, Kim JW, Sung YE, Oh SM (2004) Failure modes of silicon powder negative electrode in lithium secondary batteries. Electrochem Solid-State Lett 7:A306–A309

  8. Wang JW, He Y, Fan F, Liu XH, Xia S, Liu Y, Harris CT, Li H, Huang JY, Mao SX, Zhu T (2013) Two-phase electrochemical lithiation in amorphous silicon. Nano Lett 13:709–715

  9. Chan CK, Patel PN, O’Connell MC, Korgel BA, Cui Y (2010) Solution-grown silicon nanowires for lithiumion battery anodes. ACS Nano 4:1443–1450

  10. Ge M, Rong J, Fang X, Zhou C (2012) Porous doped silicon nanowires for lithium ion battery anode with long cycle life. Nano Lett 12:2318–2323

  11. Wen Z, Lu G, Mao S, Kim H, Cui S, Yu K, Huang X, Hurley PT, Mao O, Chen J (2013) Silicon nanotube anode for lithium-ion batteries. Electrochem Commun 29:67–70

  12. Kim H, Cho J (2008) Superior lithium electroactive mesoporous Si@ Carbon core− shell nanowires for lithium battery anode material. Nano Lett 8:3688–3691

  13. Yao Y, McDowell MT, Ryu I, Wu H, Liu N, Hu L, Nix WD, Cui Y (2011) Interconnected silicon hollow nanospheres for lithium-ion battery anodes with long cycle life. Nano Lett 11:2949–2954

  14. Chen D, Mei X, Ji G, Lu M, Xie J, Lu J, Lee JY (2012) Reversible lithium ion storage in silver treated nanoscale hollow porous silicon particles. Angew Chem 51:2409–2413

  15. Gowda SR, Pushparaj V, Herle S, Girishkumar G, Gordon JG, Gullapalli H, Zhan X, Ajayan PM, Reddy AL (2012) Three-dimensionally engineered porous silicon electrodes for Li ion batteries. Nano Lett 12:6060–6065

  16. Xia F, Kim SB, Cheng H, Lee JM, Song T, Huang Y, Rogers JA, Paik U, Park WI (2013) Facile synthesis of free-standing silicon membranes with three-dimensional nanoarchitecture for anodes of lithium ion batteries. Nano Lett 13:3340–3346

  17. Kovalenko I, Zdyrko B, Magasinski A, Hertzberg B, Milicev Z, Burtovyy R, Luzinov I, Yushin G (2011) A major constituent of brown algae for use in high-capacity Li-ion batteries. Science 334:75–79

  18. Koo B, Kim H, Cho Y, Lee KT, Choi NS, Cho J (2012) A highly cross linked polymeric binder for high performance silicon negative electrodes in lithium ion batteries. Angew Chem 51:8762–8767

  19. Gu P, Cai R, Zhou Y, Shao Z (2010) Si/C composite lithium-ion battery anodes synthesized from coarse silicon and citric acid through combined ball milling and thermal pyrolysis. Electrochim Acta 55:3876–3883

  20. Zhao X, Hayner CM, Kung MC, Kung HH (2011) In plane vacancy enabled high power Si–graphene composite electrode for lithium ion batteries. Adv Energy Mater 1:1079–1084

  21. Hwa Y, Kim WS, Hong SH, Sohn HJ (2012) High capacity and rate capability of core–shell structured nano-Si/C anode for Li-ion batteries. Electrochim Acta 71:201–205

  22. Ru Y, Evans DG, Zhu H, Yang W (2014) Facile fabrication of yolk–shell structured porous Si–C microspheres as effective anode materials for Li-ion batteries. RSC Adv 4:71–75

  23. Chabot V, Feng K, Park HW, Hassan FM, Elsayed AR, Yu A, Xiao X, Chen Z (2014) Graphene wrapped silicon nanocomposites for enhanced electrochemical performance in lithium ion batteries. Electrochim Acta 130:127–134

  24. Chew SY, Guo ZP, Wang JZ, Chen J, Munroe P, Ng SH, Zhao L, Liu HK (2007) Novel nanosilicon/polypyrrole composites for lithium storage. Electrochem Commun 9:941–946

  25. Jeong JM, Choi BG, Lee SC, Lee KG, Chang SJ, Han YK, Lee YB, Lee HU, Kwon S, Lee G, Lee CS, Huh YS (2013) Hierarchical hollow spheres of Fe2O3 @polyaniline for lithium ion battery anodes. Adv Mater 25:6250–6255

    Article  CAS  Google Scholar 

  26. Cai JJ, Zuo PJ, Cheng XQ, Xu YH, Yin GP (2010) Nano-silicon/polyaniline composite for lithium storage. Electrochem Commun 12:1572–1575

  27. Wu H, Yu G, Pan L, Liu N, McDowell MT, Bao Z, Cui Y (2013) Stable Li-ion battery anodes by in-situ polymerization of conducting hydrogel to conformally coat silicon nanoparticles. Nat Commun 4:1943

  28. Li GC, Li GR, Ye SH, Gao XP (2012) A polyaniline-coated sulfur/carbon composite with an enhanced high-rate capability as a cathode material for lithium/sulfur batteries. Adv Energy Mater 2:1238–1245

  29. Ryu KS, Kim KM, Kang SG, Joo J, Chang SH (2000) Comparison of lithium//polyaniline secondary batteries with different dopants of HCl and lithium ionic salts. J Power Sources 88:197–201

    Article  CAS  Google Scholar 

  30. Jeong CK, Jung JH, Kim BH, Lee SY, Lee DE, Jang SH, Ryu KS, Joo J (2001) Electrical, magnetic, and structural properties of lithium salt doped polyaniline. Synth Met 117:99–103

  31. McDowell MT, Lee SW, Ryu I, Wu H, Nix WD, Choi JW, Cui Y (2011) Novel size and surface oxide effects in silicon nanowires as lithium battery anodes. Nano Lett 11:4018–4025

  32. Yu BC, Hwa Y, Park CM, Kim JH, Sohn HJ (2013) Effect of oxide layer thickness to nano–Si anode for Li-ion batteries. RSC Adv 3:9408–9413

  33. Wang DS, Gao MX, Pan H, Liu YF, Wang JH, Li SQ, Ge HW (2014) Enhanced cycle stability of micro-sized Si/C anode material with low carbon content fabricated via spray drying and in situ carbonization. J Alloys Compd 604:130–136

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Acknowledgments

This work was financially supported by the Natural Science Foundation of China (11372217) and the Tianjin Committee of Science and Technology (14JCZDJC32400).

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Correspondence to Zhongqiang Shan.

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Feng, M., Tian, J., Xie, H. et al. Nano-silicon/polyaniline composites with an enhanced reversible capacity as anode materials for lithium ion batteries. J Solid State Electrochem 19, 1773–1782 (2015). https://doi.org/10.1007/s10008-015-2807-x

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  • DOI: https://doi.org/10.1007/s10008-015-2807-x

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