Journal of Materials Science

, Volume 54, Issue 6, pp 4798–4810 | Cite as

Porous carbon-coated ball-milled silicon as high-performance anodes for lithium-ion batteries

  • Joseph Nzabahimana
  • Peng Chang
  • Xianluo HuEmail author
Energy materials


Si-based anodes are promising candidates for high-performance lithium-ion batteries (LIBs) because they can offer the highest theoretical capacity over conventional graphite-based anodes used in commercial LIBs. However, the large volume change of Si upon cycling results in the degradation of structural integrity and electrode rapid capacity decay. These issues limit the practical applications of Si-based anodes in LIBs. Therefore, porous Si electrodes exhibiting excellent electrochemical performance can be used as anodes in high-energy density LIBs. In this work, we used commercially cheap microsized Si powders to synthesize porous Si via high-energy ball milling and etching processes. The milling time has a significant impact on the morphology, crystallinity, and electrochemical performance of the as-prepared samples. Structural and morphological analyses indicate that the high-energy ball milling greatly reduces the particle size of Si, and on the other hand increases the specific surface area. Porous Si electrodes with pore size of ~ 20 nm were successfully prepared. The 2h-milled porous Si coated with a uniform carbon layer of ~ 4.5 nm exhibits high reversible capacities of 1016.1 and 834.1 mAh g−1 at 1000 and 2000 mA g−1, respectively, over 200 cycles with high coulombic efficiency (> 99.5%), as well as stable cycling. The preparation process is simple, and can be regarded as an alternative route for synthesizing high-performance Si-based anodes for LIBs.



This work was supported by Ministry of Science and Technology of the People’ s Republic of China (2015AA034601), National Natural Science Foundation of China (51772116, 51472098, and 51522205), and the fund for Academic Frontier Youth Team of HUST. The authors thank the Analytical and Testing Center of HUST for XRD, SEM, and other measurements.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

10853_2018_3164_MOESM1_ESM.doc (20.2 mb)
Supplementary material 1 (DOC 20641 kb)


  1. 1.
    Liu N, Wu H, McDowell MT et al (2012) A yolk-shell design for stabilized and scalable Li-ion battery alloy anodes. Nano Lett 12:3315–3321Google Scholar
  2. 2.
    Kang K, Meng YS, Bréger J et al (2006) Electrodes with high power and high capacity for rechargeable lithium batteries. Science 311:977–981Google Scholar
  3. 3.
    Holzapfel M, Buqa H, Scheifele W et al (2005) A new type of nano-sized silicon/carbon composite electrode for reversible lithium insertion. Chem Commun 12:1566–1568Google Scholar
  4. 4.
    Luo W, Wang Y, Wang L et al (2016) Silicon/mesoporous carbon/crystalline TiO2 nanoparticles for highly stable lithium storage. ACS Nano 10:10524–10532Google Scholar
  5. 5.
    Dunn B, Kamath H, Tarascon J-M (2011) Electrical energy storage for the grid: a battery of choices. Science 334:928–935Google Scholar
  6. 6.
    Cho J, Picraux ST (2014) Silicon nanowire degradation and stabilization during lithium cycling by SEI layer formation. Nano Lett 14:3088–3095Google Scholar
  7. 7.
    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 55:3876–3883Google Scholar
  8. 8.
    Liu D-H, Li W-H, Zheng Y-P et al (2018) In situ encapsulating α-MnS into N, S-codoped nanotube-like carbon as advanced anode material: α → β phase transition promoted cycling stability and superior Li/Na-storage performance in half/full cells. Adv Mater 30:1706317Google Scholar
  9. 9.
    Chan CK, Peng H, Liu G et al (2008) High-performance lithium battery anodes using silicon nanowires. Nat Nanotechnol 3:31–35Google Scholar
  10. 10.
    Lyu F, Sun Z, Nan B et al (2017) Low-cost and novel Si-based gel for Li-ion batteries. ACS Appl Mater Interfaces 9:10699–10707Google Scholar
  11. 11.
    Rahman MA, Wong YC, Song G, Wen C (2015) A review on porous negative electrodes for high performance lithium-ion batteries. J Porous Mater 22:1313–1343Google Scholar
  12. 12.
    Cui L-F, Ruffo R, Chan CK et al (2008) Crystalline-amorphous core–shell silicon nanowires for high capacity and high current battery electrodes. Nano Lett 9:491–495Google Scholar
  13. 13.
    He W, Tian H, Xin F, Han W (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
  14. 14.
    Tian H, Tan X, Xin F et al (2015) Micro-sized nano-porous Si/C anodes for lithium ion batteries. Nano Energy 11:490–499Google Scholar
  15. 15.
    Saint J, Morcrette M, Larcher D et al (2007) Towards a fundamental understanding of the improved electrochemical performance of silicon-carbon composites. Adv Funct Mater 17:1765–1774Google Scholar
  16. 16.
    Chen Y, Qian J, Cao Y et al (2012) Green synthesis and stable Li-storage performance of FeSi2/Si@C nanocomposite for lithium-ion batteries. ACS Appl Mater Interfaces 4:3753–3758Google Scholar
  17. 17.
    Chen Y, Nie M, Lucht BL et al (2014) High capacity, stable silicon/carbon anodes for lithium-ion batteries prepared using emulsion-templated directed assembly. ACS Appl Mater Interfaces 6:4678–4683Google Scholar
  18. 18.
    Ge M, Rong J, Fang X et al (2013) Scalable preparation of porous silicon nanoparticles and their application for lithium-ion battery anodes. Nano Res 6:174–181Google Scholar
  19. 19.
    Lee WW, Lee J-M (2014) Novel synthesis of high performance anode materials for lithium-ion batteries (LIBs). J Mater Chem A 2:1589–1626Google Scholar
  20. 20.
    Liu X, Gao Y, Jin R et al (2014) Scalable synthesis of si nanostructures by low-temperature magnesiothermic reduction of silica for application in lithium ion batteries. Nano Energy 4:31–38Google Scholar
  21. 21.
    Su L, Jing Y, Zhou Z (2011) Li ion battery materials with core–shell nanostructures. Nanoscale 3:3967–3983Google Scholar
  22. 22.
    Aricò AS, Bruce P, Scrosati B et al (2005) Nanostructured materials for advanced energy conversion and storage devices. Nat Mater 4:366–377Google Scholar
  23. 23.
    Wang W, Kumta PN (2010) Nanostructured hybrid silicon/carbon nanotube heterostructures: reversible high-capacity lithium-ion anodes. ACS Nano 4:2233–2241Google Scholar
  24. 24.
    Zhu B, Liu N, McDowell M et al (2015) Interfacial stabilizing effect of ZnO on Si anodes for lithium ion battery. Nano Energy 13:620–625Google Scholar
  25. 25.
    Bang BM, Kim H, Song H-K et al (2011) Scalable approach to multi-dimensional bulk Si anodes via metal-assisted chemical etching. Energy Environ Sci 4:5013–5019Google Scholar
  26. 26.
    Wu H, Cui Y (2012) Designing nanostructured Si anodes for high energy lithium ion batteries. Nano Today 7:414–429Google Scholar
  27. 27.
    Song T, Xia J, Lee JH et al (2010) Arrays of sealed silicon nanotubes as anodes for lithium ion batteries. Nano Lett 10:1710–1716Google Scholar
  28. 28.
    Huang S, Cheong LZ, Wang D, Shen C (2017) Nanostructured phosphorus doped silicon/graphite composite as anode for high-performance lithium-ion batteries. ACS Appl Mater Interfaces 9:23672–23678Google Scholar
  29. 29.
    Zhu B, Jin Y, Tan Y et al (2015) Scalable production of Si nanoparticles directly from low grade sources for lithium-ion battery anode. Nano Lett 15:5750–5754Google Scholar
  30. 30.
    Yang Y, Yang X, Chen S et al (2017) Rational design of hierarchical carbon/mesoporous silicon composite sponges as high-performance flexible energy storage electrodes. ACS Appl Mater Interfaces 9:22819–22825Google Scholar
  31. 31.
    Zhou X, Yin YX, Cao AM et al (2012) Efficient 3D conducting networks built by graphene sheets and carbon nanoparticles for high-performance silicon anode. ACS Appl Mater Interfaces 4:2824–2828Google Scholar
  32. 32.
    Li J-Y, Xu Q, Li G et al (2017) Research progress regarding Si-based anode materials towards practical application in high energy density Li-ion batteries. Mater Chem Front 1(9):1691–1708. Google Scholar
  33. 33.
    Agyeman DA, Song K, Lee GH et al (2016) Carbon-coated Si nanoparticles anchored between reduced graphene oxides as an extremely reversible anode material for high energy-density Li-ion battery. Adv Energy Mater 6:1–10Google Scholar
  34. 34.
    Liu XH, Zhong L, Huang S et al (2012) Size-dependent fracture of silicon nanoparticles during lithiation. ACS Nano 6:1522–1531Google Scholar
  35. 35.
    Hwa Y, Kim WS, Yu BC et al (2014) Facile synthesis of Si nanoparticles using magnesium silicide reduction and its carbon composite as a high-performance anode for Li ion batteries. J Power Sources 252:144–149Google Scholar
  36. 36.
    Ge M, Rong J, Fang X, Zhou C (2012) Porous doped silicon nanowires for lithium ion battery anode with long cycle life. Nano Energy 12:2318–2323Google Scholar
  37. 37.
    Cook JB, Kim HS, Lin TC et al (2017) Tuning porosity and surface area in mesoporous silicon for application in Li-ion battery electrodes. ACS Appl Mater Interfaces 9:19063–19073Google Scholar
  38. 38.
    Ge M, Lu Y, Ercius P et al (2014) Large-scale fabrication, 3D tomography, and Lithium-ion battery application of porous silicon. Nano Lett 14:261–268Google Scholar
  39. 39.
    Yang X, Shi C, Zhang L et al (2013) Preparation of three dimensional porous silicon with fluoride-free method and its application in lithium ion batteries. ECS Solid State Lett 2:M53–M56Google Scholar
  40. 40.
    Yao Y, Mcdowell MT, Ryu I et al (2011) Interconnected silicon hollow nanospheres for lithium-ion battery anodes with long cycle life. Nano Lett 11:2949–2954Google Scholar
  41. 41.
    Park MH, Kim MG, Joo J et al (2009) Silicon nanotube battery anodes. Nano Lett 9:3844–3847Google Scholar
  42. 42.
    Xie J, Tong L, Su L et al (2017) Core-shell yolk-shell Si@C@Void@C nanohybrids as advanced lithium ion battery anodes with good electronic conductivity and corrosion resistance. J Power Sources 342:529–536Google Scholar
  43. 43.
    Huang X, Sui X, Yang H et al (2018) HF-free synthesis of Si/C yolk/shell anodes for lithium-ion batteries. J Mater Chem A 6:2593–2599Google Scholar
  44. 44.
    Ma Y, Tang H, Zhang Y et al (2017) Facile synthesis of Si-C nanocomposites with yolk-shell structure as an anode for lithium-ion batteries. J Alloys Compd 704:599–606Google Scholar
  45. 45.
    Ryu I, Choi JW, Cui Y, Nix WD (2011) Size-dependent fracture of Si nanowire battery anodes. J Mech Phys Solids 59:1717–1730Google Scholar
  46. 46.
    Zuo P, Yin G, Ma Y (2007) Electrochemical stability of silicon/carbon composite anode for lithium ion batteries. Electrochim Acta 52:4878–4883Google Scholar
  47. 47.
    Gu M, Li Y, Li X et al (2012) In situ TEM study of lithiation behavior of silicon nanoparticles attached to and embedded in a carbon matrix. ACS Nano 6:8439–8447Google Scholar
  48. 48.
    Zhou XY, Tang JJ, Yang J et al (2013) Silicon@carbon hollow core–shell heterostructures novel anode materials for lithium ion batteries. Electrochim Acta 87:663–668Google Scholar
  49. 49.
    Xu Q, Li J-Y, Sun J-K et al (2017) Watermelon-inspired Si/C microspheres with hierarchical buffer structures for densely compacted lithium-ion battery anodes. Adv Energy Mater 7:1601481Google Scholar
  50. 50.
    Wang J, Liu D-H, Wang Y-Y et al (2016) Dual-carbon enhanced silicon-based composite as superior anode material for lithium ion batteries. J Power Sources 307:738–745Google Scholar
  51. 51.
    Yi R, Dai F, Gordin ML et al (2013) Micro-sized Si-C composite with interconnected nanoscale building blocks as high-performance anodes for practical application in lithium-ion batteries. Adv Energy Mater 3:295–300Google Scholar
  52. 52.
    Li C, Shi T, Yoshitake H, Wang H (2016) Improved performance in micron-sized silicon anodes by in situ polymerization of acrylic acid-based slurry. J Mater Chem A 4:16982–16991Google Scholar
  53. 53.
    Liu N, Lu Z, Zhao J et al (2014) A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes. Nat Nanotechnol 9:187–192Google Scholar
  54. 54.
    Gauthier M, Mazouzi D, Reyter D et al (2013) A low-cost and high performance ball-milled Si-based negative electrode for high-energy Li-ion batteries. Energy Environ Sci 6:2145–2155Google Scholar
  55. 55.
    Bruce PG, Scrosati B, Tarascon JM (2008) Nanomaterials for rechargeable lithium batteries. Angew Chemie Int Ed 47:2930–2946Google Scholar
  56. 56.
    Hou SC, Su YF, Chang CC et al (2017) The synergistic effects of combining the high energy mechanical milling and wet milling on Si negative electrode materials for lithium ion battery. J Power Sources 349:111–120Google Scholar
  57. 57.
    Feng X, Yang J, Bie Y et al (2014) Nano/micro-structured Si/CNT/C composite from nano-SiO2 for high power lithium ion batteries. Nanoscale 6:12532–12539Google Scholar
  58. 58.
    Xu Q, Sun J-K, Yin Y, Guo Y-G (2018) Facile synthesis of Blocky SiOx/C with graphite-like structure for high-performance lithium-ion battery anodes. Adv Funct Mater 28:1705235Google Scholar
  59. 59.
    Luo W, Wang Y, Chou S et al (2016) Critical thickness of phenolic resin-based carbon interfacial layer for improving long cycling stability of silicon nanoparticle anodes. Nano Energy 27:255–264Google Scholar
  60. 60.
    Yadav TP, Yadav RM, Singh DP (2012) Mechanical milling: a top down approach for the synthesis of nanomaterials and nanocomposites. Nanosci Nanotechnol 2:22–48Google Scholar
  61. 61.
    Wang J, Lü H-Y, Fan C-Y et al (2017) Ultrafine nano-Si material prepared from NaCl-assisted magnesiothermic reduction of scalable silicate: graphene-enhanced Li-storage properties as advanced anode for lithium-ion batteries. J Alloys Compd 694:208–216Google Scholar
  62. 62.
    Chen Y, Liu L, Xiong J et al (2015) Porous Si nanowires from cheap metallurgical silicon stabilized by a surface oxide layer for lithium ion batteries. Adv Funct Mater 25:6701–6709Google Scholar
  63. 63.
    Xia H, Wang Y, Lin J, Lu L (2012) Hydrothermal synthesis of MnO2/CNT nanocomposite with a CNT core/porous MnO2 sheath hierarchy architecture for supercapacitors. Nanoscale Res Lett 7:1–10Google Scholar
  64. 64.
    Zhong H, Zhan H, Zhou Y (2014) Synthesis of nanosized mesoporous silicon by magnesium-thermal method used as anode material for lithium ion battery. J Power Sources 262:10–14Google Scholar
  65. 65.
    Kim H, Han B, Choo J, Cho J (2008) Three-dimensional porous silicon particles for use in high-performance lithium secondary batteries. Angew Chemie 120:10305–10308Google Scholar
  66. 66.
    Casimir A, Zhang H, Ogoke O et al (2016) Silicon-based anodes for lithium-ion batteries: effectiveness of materials synthesis and electrode preparation. Nano Energy 27:359–376Google Scholar
  67. 67.
    Vlad A, Reddy ALM, Ajayan A et al (2012) Roll up nanowire battery from silicon chips. Proc Natl Acad Sci 109:15168–15173Google Scholar
  68. 68.
    Yen YC, Chao SC, Wu HC, Wu NL (2009) Study on solid-electrolyte-interphase of Si and C-coated si electrodes in lithium cells. J Electrochem Soc 156:A95–A102Google Scholar
  69. 69.
    Rong J, Masarapu C, Ni J et al (2010) Tandem structure of porous silicon film on single-walled carbon nanotube macrofilms for lithium-ion battery applications. ACS Nano 4:4683–4690Google Scholar
  70. 70.
    Lee JI, Lee KT, Cho J et al (2012) Chemical-assisted thermal disproportionation of porous silicon monoxide into silicon-based multicomponent systems. Angew Chemie 51:2767–2771Google Scholar
  71. 71.
    Song J, Chen S, Zhou M et al (2014) Micro-sized silicon–carbon composites composed of carbon-coated sub-10 nm Si primary particles as high-performance anode materials for lithium-ion batteries. J Mater Chem A 2:1257–1262Google Scholar
  72. 72.
    Nie P, Liu X, Fu R et al (2017) Mesoporous silicon anodes by using polybenzimidazole derived pyrrolic N-enriched carbon toward high-energy Li-ion batteries. ACS Energy Lett 2:1279–1287Google Scholar
  73. 73.
    Xu ZL, Liu X, Luo Y et al (2017) Nanosilicon anodes for high performance rechargeable batteries. Prog Mater Sci 90:1–44Google Scholar
  74. 74.
    Kovalenko I, Zdyrko B, Magasinski A et al (2011) A major constituent of brown algae for use in high-capacity li-ion batteries. Science 334:75–79Google Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.State Key Laboratory of Materials Processing and Die and Mould Technology, School of Materials Science and EngineeringHuazhong University of Science and TechnologyWuhanChina

Personalised recommendations