Journal of Solid State Electrochemistry

, Volume 23, Issue 12, pp 3363–3372 | Cite as

The effect of carbon coating on graphite@nano-Si composite as anode materials for Li-ion batteries

  • Wenping Liu
  • Huarui XuEmail author
  • Haiqing QinEmail author
  • Yanlu Lv
  • Feng Wang
  • Guisheng Zhu
  • Feng Lin
  • Lihui Wang
  • Chengyuan Ni
Original Paper


The graphite@nano-Si@C composite was prepared by a designed hot reactor with stirring function by coating pitch carbon on the surface of graphite@nano-Si composite, and the effect of the carbon coating on the structure and electrochemical properties of the composite was also investigated by physical characterization and electrochemical measurement technologies. The pitch carbon coating can decrease the surface area of graphite@nano-Si@C composite, and there are no silicon nanopowders bared on the surface. The first discharge/charge capacity of graphite@nano-Si composite is 644.6 and 582.1 mAh g−1 with initial coulombic efficiency of 90.31%, and the capacity retention after 300 cycles is 66.03%. The pitch carbon coating layer impedes delithiation reaction leading to the increase of delithiation voltage, which also affects the charge transport ability of graphite@nano-Si@C composite before activation. However, the capacity retention of graphite@nano-Si@C composite corresponding to 10 wt% and 20 wt% pitch addition after 300 cycles reaches 80.90% and 84.51% with first discharge capacity of 623.6 and 618.8 mAh g−1, respectively, which is attributed to the pitch carbon coating layer can stable the SEI film and buffer volume expansion to enhance the cycle performance.


Inductively coupled plasma technology Silicon nanopowders Carbon coating graphite@nano-Si@C composite Li-ion batteries 


Funding information

This work was supported by the Guangxi Innovation-Driven Development Project (AA17204022, AA18118001), the Science and Technology Plan of China Nonferrous Group (2016KJJH03), and the Scientific and Technological Plan of Guilin City (201607010322).


  1. 1.
    Etacheri V, Marom R, Elazari R, Salitra G, Aurbach D (2011) Challenges in the development of advanced Li-ion batteries: a review. Energy Environ Sci 4:3243–3262Google Scholar
  2. 2.
    Wang MY, Yin L, Li MQ, Luo SH, Wang C (2019) Low-cost heterogeneous dual-carbon shells coated silicon monoxide porous composites as anodes for high-performance lithium-ion batteries. J Colloid Interf Sci 549:225–235Google Scholar
  3. 3.
    Zuo XX, Zhu J, Müller-Buschbaum P, Cheng YJ (2017) Silicon based lithium-ion battery anodes: a chronicle perspective review. Nano Energy 31:113–143Google Scholar
  4. 4.
    Lu J, Chen Z, Pan F, Cui Y, Amine K (2018) High-performance anode materials for rechargeable lithium-ion batteries. Electrochem Energy Rev 1:35–53Google Scholar
  5. 5.
    Dong QC, Yang J, Wu MY, Zhou XY, Zhang YZ, Wang WJ, Si WL, Huang W (2018) Template-free synthesis of cobalt silicate nanoparticles decorated nanosheets for high performance lithium ion batteries. ACS Sustain Chem Eng 6:15591–15597Google Scholar
  6. 6.
    Jin Y, Zhu B, Lu ZD, Liu N, Zhu J (2017) Challenges and recent progress in the development of Si anodes for lithium-ion battery. Adv Energy Mater 7:1700715Google Scholar
  7. 7.
    Trill JH, Tao C, Winter M, Passerini S, Eckert H (2011) NMR investigations on the lithiation and delithiation of nanosilicon-based anodes for Li-ion batteries. J Solid State Electrochem 15(2):349–356Google Scholar
  8. 8.
    Xin X, Yao X, Zhang Y, Liu Z, Xu X (2012) Si/C nanocomposite anode materials by freeze-drying with enhanced electrochemical performance in lithium-ion batteries. J Solid State Electrochem 16(8):2733–2738Google Scholar
  9. 9.
    Lu ZD, Liu N, Lee HW, Zhao J, Li WY, LiY Z, Cui Y (2015) Nonfilling carbon coating of porous silicon micrometer-sized particles for high-performance lithium battery anodes. ACS Nano 9:2540–2547PubMedGoogle Scholar
  10. 10.
    Wang B, Li W, Wu T, Guo J, Wen Z (2018) Self-template construction of mesoporous silicon submicrocube anode for advanced lithium ion batteries. Energy Storage Mater 15:139–147Google Scholar
  11. 11.
    Wang GQ, Xu B, Shi J, Lei XL, Ouyang CY (2018) Confined Li ion migration in the silicon-graphene complex system: an ab initio investigation. Appl Surf Sci 436:505–510Google Scholar
  12. 12.
    BerlaL A, Lee SW, Cui Y, Nix WD (2015) Mechanical behavior of electrochemically lithiated silicon. J Power Sources 273:41–51Google Scholar
  13. 13.
    Zhou Y, Guo H, Yong Y, Wang Z, Li X, Zhou R (2017) Introducing reduced grapheme oxide to improve the electrochemical performance of silicon-based materials encapsulated by carbonized polydopamine layer for lithium ion batteries. Mater Lett 195:164–167Google Scholar
  14. 14.
    Zhou Y, Guo HJ, Yan GH, Wang ZX, Li XH, Yang ZW, Zheng AX, Wang JX (2018) Fluidized bed reaction towards crystalline embedded amorphous Si anode with much enhanced cycling stability. Chem Commun 54(30):3755–3758Google Scholar
  15. 15.
    Roy AK, Zhong M, Schwab MG, Binder A, Venkataraman SS, Tomovic Z (2016) Preparation of a binder-free three-dimensional carbon foam/silicon composite as potential material for lithium ion battery anodes. ACS Appl Mater Interfaces 8:7343–7348PubMedGoogle Scholar
  16. 16.
    Fang M, Wang Z, Chen X, Guan S (2018) Sponge-like reduced graphene oxide/silicon/carbon nanotube composites for lithium ion batteries. Appl Surf Sci 436:345–353Google Scholar
  17. 17.
    Chen HD, Shen KX, Hou XH, Zhang GZ, Wang SF (2019) Si-based anode with hierarchical protective function and hollow ring-like carbon matrix for high performance lithium ion batteries. Appl Surf Sci 470:496–506Google Scholar
  18. 18.
    Ma Y, Younesi R, Pan R, Liu C, Zhu J, Wei B, Edström K (2016) Constraining Si particles within graphene foam monolith: interfacial modification for high-performance Li+ storage and flexible integrated configuration. Adv Funct Mater 26:6797–6806Google Scholar
  19. 19.
    Kaushik K, Marco-Tulio FR, Stephen ET, Ilya AS, Daniel PA (2018) Calendar-life versus cycle-life aging of lithium-ion cells with silicon-graphite composite electrodes. Electrochim Acta 280:221–228Google Scholar
  20. 20.
    Li Y, Xu GJ, Yao YF, Xue LG, Zhang S, Lu Y, Toprakci O, Zhang X (2013) Improvement of cyclability of silicon-containing carbon nanofiber anodes for lithium-ion batteries by employing succinic anhydride as an electrolyte additive. J Solid State Electrochem 17(5):1393–1399Google Scholar
  21. 21.
    Jing SL, Jiang H, Hu YJ, Shen JH (2015) Face-to-face contact and open-void coinvolved Si/C nanohybrids lithium-ion battery anodes with extremely long cycle life. Adv Funct Mater 25:5395–5401Google Scholar
  22. 22.
    Zhang R, Du Y, Li D, Shen D, Yang J, Guo Z, Liu HK, Elzatahry AA, Zhao D (2014) Highly reversible and large lithium storage in mesoporoussi/c nanocomposite anodes with silicon nanoparticles embedded in a carbon framework. Adv Mater 26:6749–6755PubMedGoogle Scholar
  23. 23.
    Zhang X, Qiu X, Kong D, Zhou L, Li Z, Li X, Zhi L (2017) Silicene flowers: a dual stabilized silicon building block for high-performance lithium battery anodes. ACS Nano 11(7):7476–7484PubMedGoogle Scholar
  24. 24.
    LiY CB, Li T, Kang L, Xu S, Zhang D, Xie L, Liang W (2016) One-step synthesis of hollow structured Si/C composites based on expandable microspheres as anodes for lithium ion batteries. Electrochem Commun 72:69–73Google Scholar
  25. 25.
    Xu ZL, Zhang B, Kim JK (2014) Electrospun carbon nanofiber anodes containing monodispersed Si nanoparticles and graphene oxide with exceptional high rate capacities. Nano Energy 6:27–35Google Scholar
  26. 26.
    Zhang F, Yang X, Xie Y, Yi N, Huang Y, Chen Y (2015) Pyrolytic carbon-coated Si nanoparticles on elastic graphene framework as anode materials for high-performance lithium-ion batteries. Carbon 82:161–167Google Scholar
  27. 27.
    Chen HD, Hou XH, Chen FM, Wang SF, Wu B, Ru Q, Qin HQ, Xia YC (2018) Milled flake graphite/plasma nano-silicon@carbon composite with void sandwich structure for high performance as lithium ion battery anode at high temperature. Carbon 130:433–440Google Scholar
  28. 28.
    Yu ZZ, Tian BB, LiY FDY, Yang DG, Zhu GS, Cai M, Yan DL (2019) Lithium titanate matrix-supported nanocrystalline silicon film as an anode for lithium-ion batteries. ACS Appl Mater Interfaces 11:534–540PubMedGoogle Scholar
  29. 29.
    Liang GM, Qin XY, Zou JS, Luo LY, Wang YZ, Wu MY, Zhu H, Chen GH, Kang FY, Li BH (2018) Electrosprayed silicon-embedded porous carbon microspheres as lithium-ion battery anodes with exceptional rate capacities. Carbon 127:424–431Google Scholar
  30. 30.
    Wang M, Xiao X (2016) Investigation of the chemo-mechanical coupling in lithiation/delithiation of amorphous Si through simulations of Si thin films and Si nanospheres. J Powers Sources 326:365–376Google Scholar
  31. 31.
    Kaushik K, Ilya AS, Richard TH, Cameron P, Javier B, Daniel PA (2017) Auger electrons as probes for composite micro- and nanostructured materials: application to solid electrolyte interphases in graphite and silicon-graphite electrodes. J Phys Chem C 121:23333–23346Google Scholar
  32. 32.
    Laïk B, Ung D, Caillard A, Cojocaru CS, Pribat D, Pereira-Ramos JP (2010) An electrochemical and structural investigation of silicon nanowires as negative electrode for Li-ion batteries. J Solid State Electrochem 14(10):1835–1839Google Scholar
  33. 33.
    Erwin H, Harald S (2018) Lithium permeability increase in nanosized amorphous silicon layers. J Phys Chem C 122:28528–28536Google Scholar
  34. 34.
    Javier B, Ilya AS, James AG, Matilda K, Daniel PA (2017) Capacity fade and its mitigation in Li-ion cells with silicon-graphite electrodes. J Phys Chem C 121:20640–20649Google Scholar
  35. 35.
    Wang T, Zhu J, Chen Y, Yang HG, Qin Y, Li F, Cheng QF, Yu XZ, Xu Z, Lu BG (2017) Large-scale production of silicon nanoparticles@graphene embedded in nanotubes as ultra-robust battery anodes. J Mater Chem A 5:4809–4817Google Scholar
  36. 36.
    Aliya M, Albina J, Myung ST, Kim SS, Zhumabay B (2018) A mini-review on the development of Si-based thin film anodes for Li-ion batteries. Materials Today Energy 9:49–66Google Scholar
  37. 37.
    Yi Z, Lin N, Xu TJ, Qian YT (2018) TiO2 coated Si/C interconnected microsphere with stable framework and interface for high-rate lithium storage. Chem Eng J347:214–222Google Scholar
  38. 38.
    So KS, Lee HJ, Kim TH (2014) Synthesis of silicon nanopowderss from silane gas by RF thermal plasma. Phys. Status Solidi A 211:310–315Google Scholar
  39. 39.
    Chen HD, Wang ZL, Hou XH, Fu LJ, Wang SF, Hu XQ, Qin HQ, Wu YP, Ru QP, Liu X, Hu SJ (2017) Mass-producible method for preparation of a carbon-coated graphite@plasmanano-silicon@carbon composite with enhanced performance as lithium ion battery anode. Electrochim Acta 249:113–121Google Scholar
  40. 40.
    Yana M, David Z (2017) Operando plasmon-enhanced Raman spectroscopy in silicon anodes for Li-ion battery. J Nanoparticle Res 19:372Google Scholar
  41. 41.
    Yoshifumi I, Kazunori H, Kaveh E, Katsuhiko S, GuoQX HZJ, Toshihiro A, David JS (2014) Fabrication of nanograined silicon by high-pressure torsion. J Mater Sci 49:6565–6569Google Scholar
  42. 42.
    Michan AL, Leskes M, Grey CP (2016) Voltage dependent solid electrolyte interphase formation in silicon electrodes: monitoring the formation of organic decomposition products. Chem Mater 28:385–398Google Scholar
  43. 43.
    Wang HR, Chew HB (2017) Nanoscale mechanics of the solid electrolyte interphase on lithiated-silicon electrodes. ACS Appl Mater Interfaces 9:25662–25667PubMedGoogle Scholar
  44. 44.
    Zhou Y, Guo HJ, Wang ZX, Li XH, Zhou R, Peng WJ (2017) Improved electrochemical performance of Si/C material based on the interface stability. J Alloy Compd 725:1304–1312Google Scholar
  45. 45.
    Cao CT, Iwnetim IA, Eric S, Badri S, Jia CJ, Brian M, Thomas PD, Kristin AP, Steinrück HG (2019) Solid electrolyte interphase on native oxide-terminated silicon anodes for Li-ion batteries. Joule 3:762–781Google Scholar
  46. 46.
    Schroder KW, Dylla AG, Harris SJ, Webb LJ, Stevenson KJ (2014) Role of surface oxides in the formation of solid–electrolyte interphases at silicon electrodes for lithium-ion batteries. ACS Appl Mater Interfaces 6:21510–21524PubMedGoogle Scholar
  47. 47.
    He W, Tian HJ, Xin FX, Han WQ (2015) Scalable fabrication of micro-sized bulk porous Si from Fe-Si alloy as a high performance anode for lithium-ion batteries. J Mater Chem A 3:17956–17962Google Scholar
  48. 48.
    Shi L, Wang WK, Wang AB, Yuan KG, Jin ZQ, Yang YS (2015) Si nanoparticles adhering to a nitrogen-rich porous carbon framework and its application as a lithium-ion battery anode material. J Mater Chem A 3:18190–18197Google Scholar
  49. 49.
    Zhang J, Gu J, He H, Li M (2017) High-capacity nano-Si@SiOx@C anode composites for lithium-ion batteries with good cyclic stability. J Solid State Electrochem 21(8):2259–2267Google Scholar
  50. 50.
    Wang QT, Li RR, Zhou XZ, Li J, Lei ZQ (2016) Polythiophene-coated nano-silicon composite anodes with enhanced performance for lithium-ion batteries. J Solid State Electrochem 20(5):1331–1336Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Wenping Liu
    • 1
    • 2
  • Huarui Xu
    • 1
    Email author
  • Haiqing Qin
    • 2
    Email author
  • Yanlu Lv
    • 3
  • Feng Wang
    • 1
  • Guisheng Zhu
    • 1
  • Feng Lin
    • 2
    • 3
  • Lihui Wang
    • 2
  • Chengyuan Ni
    • 4
  1. 1.School of Mechanical and Electrical Engineering, Guangxi Key Laboratory of Information MaterialsGuilin University of Electronic TechnologyGuilinChina
  2. 2.National Engineering Research Center for Special Mineral Material, Guangxi Key Laboratory of super hard materialChina Nonferrous Metal (Guilin) Geology And Mining Co., LtdGuilinChina
  3. 3.College of Materials Science and EngineeringGuilin University of TechnologyGuilinChina
  4. 4.Key Laboratory of Air-driven Equipment Technology of Zhejiang Province, School of Mechanical EngineeringQuzhou UniversityQuzhouChina

Personalised recommendations