Skip to main content
Log in

Towards the realistic silicon/carbon composite for Li-ion secondary battery anode

  • Research Article
  • Published:
Journal of Applied Electrochemistry Aims and scope Submit manuscript

Abstract

A practical and inexpensive method for producing Si/C composite as ready-to-use active material for Li-ion battery anode has been developed. Three-component powders (<63 µm) were synthesized by embedding micro-sized silicon (8–24 wt%) and synthetic battery-grade graphite (60–75 wt%) in a pitch-derived carbon matrix. The procedure consisted of short mechanical milling of silicon with toluene/pitch suspension followed by mixing with graphite and final heat-treatment at 1,100 °C. X-ray diffraction was applied for determining the structural characteristics of the composite and impurities present. A series of anodes were prepared by using CMC and PVDF binder. The dispersion of silicon particles in the carbon matrix and spreading of the binder into the anodic film were monitored using the SEM–EDX technique. Lithium insertion/deinsertion performance was assessed from the galvanostatic charge–discharge characteristics using a Si/C–lithium two-electrode cell. Embedding silicon in well conductive pitch coke as well as reducing the content of carbon black as percolator allowed the first cycle irreversible capacity to be decreased to 90 mAh g−1. An initial reversible capacity of 620 mAh g−1 for 12 wt% of Si in the composite, with average capacity decay of 0.3 % per cycle, was achieved thanks to a specific composite structure as well as profitable physicochemical properties of the CMC binder. Intensive press-rolling of the anodic film allowed the packing density to be increased up to 1.35 g cm−3 (9.5 mg cm−2 at thickness of 70 µm) and, as a result, an outstanding volumetric capacity up to 670 mAh cm−3 could be achieved, without changing the cycling properties.

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.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11

Similar content being viewed by others

References

  1. Endo M, Kim YJ, Park KC (2010) Advanced battery applications of carbons. In: Beguin F, Frackowiak E (eds) Carbons for electrochemical energy storage and conversion systems. CRC Press, London, pp 469–507

    Google Scholar 

  2. Novak P, Goers D, Spahr ME (2010) Carbon materials in lithium-ion batteries. In: Beguin F, Frackowiak E (eds) Carbons for electrochemical energy storage and conversion systems. CRC Press, London, pp 263–328

    Google Scholar 

  3. Ishii Y, Fujita A, Nishida T, Yamada K (2001) High-performance anode material for lithium-ion rechargeable battery. Hitachi Chem Tech Rep 36:27–32

    Google Scholar 

  4. Zheng T, Dahn JR (1999) Application of carbon in lithium-ion batteries. In: Burchell TD (ed) Carbon materials for advanced technologies. Pergamon, Amsterdam, pp 341–387

    Chapter  Google Scholar 

  5. Yoshio M, Tsumura T, Dimov N (2005) Electrochemical behaviors of silicon based anode material. J Power Sources 146:10–14

    Article  CAS  Google Scholar 

  6. Wang GX, Ahn JH, Yao J, Bewlay S, Liu HK (2004) Nanostructured Si-C composite anodes for lithium-ion batteries. Electrochem Commun 6:689–692

    Article  CAS  Google Scholar 

  7. Chan CK, Peng H, Liu G, McIlwrath K, Zhang XF, Huggins RA, Cui Y (2008) High-performance lithium battery anodes using silicon nanowires. Nat Nanotechnol 3:31–35

    Article  CAS  Google Scholar 

  8. Miyaki Y (2005) US Patent, Patent No: US 6,908,709 B2

  9. Foster D, Wolfenstine J, Read J, Allen JL (2008) Performance of Sony’s alloy based Li-ion battery. Army Research Laboratory, ARL-TN-0319

  10. Xing W, Wilson AM, Eguchi K, Zank G, Dahn JR (1997) Pyrolyzed polysiloxanes for use as anode materials in lithium-ion batteries. J Electrochem Soc 144:2410–2416

    Article  CAS  Google Scholar 

  11. Liu Y, Hanai K, Yang J, Imanishi N, Hirano A, Takeda Y (2004) Silicon/carbon composites as anode materials for Li-ion batteries. Electrochem Solid-State Lett 7:A369–A372

    Article  CAS  Google Scholar 

  12. Liu WR, Wang JH, Wu HC, Shieh DT, Yang MH, Wu NL (2005) Electrochemical characterizations on Si and C-coated Si particle electrodes for lithium-ion batteries. J Electrochem Soc 152:A1719–A1725

    Article  CAS  Google Scholar 

  13. Holzapfel M, Buqa H, Krumelch F, Novak P, Petrat FM, Velt C (2005) Chemical vapor deposited silicon/graphite compound material as negative electrode for lithium-ion batteries. Electrochem Solid-State Lett 8:A516–A520

    Article  CAS  Google Scholar 

  14. Dimov N, Kugino S, Yoshio M (2004) Mixed silicon-graphite composites as anode material for lithium ion batteries—influence of preparation conditions on the properties of the material. J Power Sources 136:108–114

    Article  CAS  Google Scholar 

  15. Zhang Z, Wang Y, Ren W, Tan Q, Chen Y, Li H, Zhong Z, Su F (2014) Scalable synthesis of interconnected porous silicon/carbon composites by the Rochow reaction as high-performance anodes of lithium ion batteries. Angew Chem Int Edit 53:5165–5169

    CAS  Google Scholar 

  16. Yu J, Zhan H, Wang Y, Zhang Z, Chen H, Li H, Zhong Z, Su F (2013) Graphite microspheres decorated with Si particles derived from waste solid of organosilane industry as high capacity anodes for Li-ion batteries. J Power Sources 228:112–119

    Article  CAS  Google Scholar 

  17. Eker Y, Kierzek K, Raymundo-Pinero E, Machnikowski J, Beguin F (2010) Effect of electrochemical conditions on the performance worsening of Si/C composite anodes for lithium batteries. Electrochim Acta 55:729–736

    Article  CAS  Google Scholar 

  18. Wang YX, Chou SL, Kim JH, Liu HK, Dou SX (2013) Nanocomposites of silicon and carbon derived from coal tar pitch: cheap anode materials for lithium-ion batteries with long cycle life and enhanced capacity. Electrochim Acta 93:213–221

    Article  CAS  Google Scholar 

  19. Bridel JS, Azaïs T, Morcrette M, Tarascon JM, Larcher D (2010) Key parameters governing the reversibility of Si/carbon/CMC electrodes for Li-ion batteries. Chem Mater 22:1229–1241

    Article  CAS  Google Scholar 

  20. Komaba S, Shimomura K, Yabuuchi N, Ozeki T, Yui H, Konno K (2011) Study on polymer binders for high-capacity SiO negative electrode of Li-ion batteries. J Phys Chem C 115:13487–13495

    Article  CAS  Google Scholar 

  21. Li J, Lewis RB, Dahn JR (2007) Sodium arcboxymethyl cellulose: a potential binder for Si negative electrodes for Li-ion batteries. Electrochem Solid-State Lett 10:A17–A20

    Article  CAS  Google Scholar 

  22. 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. Appl Mater Interfaces 2:3004–3010

    Article  CAS  Google Scholar 

  23. Datta MK, Kumta PN (2007) Silicon, graphite and resin based hard carbon nanocomposite anodes for lithium ion batteries. J Power Sources 165:368–378

    Article  CAS  Google Scholar 

  24. Choi H, Lee W, Kim DU, Kumar S, Kim SS, Chung HS, Kim JH, Ahn YC (2010) Effect of grinding aids on the grinding energy consumed during grinding of calcite in a stirred ball mill. Miner Eng 23:54–57

    Article  CAS  Google Scholar 

  25. Dubinin MM (1989) Fundamentals of the theory of adsorption in micropores of carbon adsorbents: characteristics of their adsorption properties and microporous structures. Carbon 27:457–467

    Article  CAS  Google Scholar 

  26. Stoeckli F, López-Ramón MV, Hugi-Cleary D, Guillot A (2001) Micropore sizes in activated carbons determined from the Dubinin–Radushkevich equation. Carbon 39:1115–1116

    Article  CAS  Google Scholar 

  27. Lee JH, Kim WJ, Kim JY, Lim SH, Lee SM (2008) Spherical silicon/graphite/carbon composites as anode material for lithium-ion batteries. J Power Sources 176:353–358

    Article  CAS  Google Scholar 

  28. Obrovac MN, Krause LJ (2007) Reversible cycling of crystalline silicon powder. J Electrochem Soc 154:A103–A108

    Article  CAS  Google Scholar 

  29. Zhang Z, Zeng T, Lai Y, Jia M, Li J (2014) A comparative study of different binders and their effects on electrochemical properties of LiMn2O4 cathode in lithium ion batteries. J Power Sources 247:1–8

    Article  CAS  Google Scholar 

  30. Dimov N, Xia Y, Yoshio M (2007) Practical silicon-based composite anodes for lithium-ion batteries: fundamental and technological features. J Power Sources 171:886–893

    Article  CAS  Google Scholar 

  31. Ishii Y, Nishida T, Suda T, Kobayashi M (2006) Anode material for high energy density rechargeable lithium-ion battery. Hitachi Chem Tech Rep 47:29–32

    Google Scholar 

  32. Ota M, Izuo S, Nishikawa K, Fukunaka Y, Kusaka E, Ishii R, Selman JR (2003) Measurement of concentration boundary layer thickness development during lithium electrodeposition onto a lithium metal cathode in propylene carbonate. J Electroanal Chem 559:175–183

    Article  CAS  Google Scholar 

  33. Rosso M, Brissot C, Teyssot A, Dollé M, Sannier L, Tarascon JM, Bouchet R (2006) Dendrite short-circuit and fuse effect on Li/polymer/Li cells. Electrochim Acta 51:5334–5340

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The research was supported by the Wrocław Research Centre EIT+ within the project “The Application of Nanotechnology in Advanced Materials”—NanoMat (POIG.01.01.02-02-002/08) cofinanced from the resources of European Fund of Regional Development (PO IG 1.1.2).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Krzysztof Kierzek.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kierzek, K., Machnikowski, J. & Béguin, F. Towards the realistic silicon/carbon composite for Li-ion secondary battery anode. J Appl Electrochem 45, 1–10 (2015). https://doi.org/10.1007/s10800-014-0754-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10800-014-0754-3

Keywords

Navigation