Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Carbon-coated Fe3O4 nanospindles as solid electrolyte interface for improving graphite anodes in lithium ion batteries


This paper reports surface modification of graphite anodes using carbon coated Fe3O4 nanospindles (C–Fe3O4 NSs) with the goal of improving graphite electrode capacity and decreasing graphite degradation and irreversible capacity. A unique novel coating method based on magnetic fields was developed for coating prefabricated graphite electrodes containing conductive additives and binder. A thin layer of synthesized C–Fe3O4 NSs was coated on the surface of graphite anodes to prevent direct contact of graphite’s surface and electrolyte. The results indicate that C–Fe3O4 coating decreases growth of solid electrolyte interface (SEI) film on the surface of graphite. The C–Fe3O4 coating increases the initial discharge capacity of graphite anodes from 325 to 414 mAh g−1 and the initial Coulombic efficiency from 72 to 79%. Moreover, C–Fe3O4 coated electrodes deliver an improved reversible capacity of 240 mAh g−1 and Columbic efficiency of 99% after 40 cycles, whereas these values were 148 mAh g−1 and 97% for bare graphite. However, the impedance analysis indicates more resistance in case of C–Fe3O4 coated graphite, which is due to the low ionic conductivity of Fe3O4 compared to graphite.

Graphic abstract

This is a preview of subscription content, log in to check access.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8


  1. 1.

    Fu LJ, Liu H, Li C, Wu YP, Rahm E, Holze R, Wu HQ (2006) Surface modifications of electrode materials for lithium ion batteries. Solid State Sci 8:113

  2. 2.

    Van Schalkwijk WA, Scrosati B (2002) Advances in lithium ion batteries. Springer, New York

  3. 3.

    Candelaria SL, Shao Y, Zhou W, Li X, Xiao J, Zhang JG, Wang Y, Liu J, Li J, Cao G (2012) Nanostructured carbon for energy storage and conversion. Nano Energy 1:195

  4. 4.

    Agubra V, Fergus J (2013) Lithium ion battery anode aging mechanisms. Materials 6:1310

  5. 5.

    Moradi B, Botte GG (2016) Recycling of graphite anodes for the next generation of lithium ion batteries. J Appl Electrochem 123:46

  6. 6.

    Mauger A, Julien C (2014) Surface modifications of electrode materials for lithium-ion batteries: status and trends. Ionics 20:751

  7. 7.

    Tang Y, Zhang Y, Li W, Ma B, Chen X (2015) Rational material design for ultrafast rechargeable lithium-ion batteries. Chem Soc Rev 44:5926

  8. 8.

    Wang K-X, Li X-H, Chen J-S (2015) Surface and interface engineering of electrode materials for lithium-ion batteries. Adv Mater 27:527

  9. 9.

    Lee HY, Baek JK, Jang SW, Lee SM, Hong ST, Lee KY, Kim MH (2001) Characteristics of carbon-coated graphite prepared from mixture of graphite and polyvinylchloride as anode materials for lithium ion batteries. J Power Sources 101:206

  10. 10.

    Momose H, Honbo H, Takeuchi S, Nishimura K, Horiba T, Muranaka Y, Kozono Y, Miyadera H (1997) X-ray photoelectron spectroscopy analyses of lithium intercalation and alloying reactions on graphite electrodes. J Power Sources 68:208

  11. 11.

    Nishimura K, Honbo H, Takeuchi S, Horiba T, Oda M, Koseki M, Muranaka Y, Kozono Y, Miyadera H (1997) Design and performance of 10 Wh rechargeable lithium batteries. J Power Sources 68:436

  12. 12.

    Veeraraghavan B, Durairajan A, Haran B, Popov B, Guidotti R (2002) Study of Sn-coated graphite as anode material for secondary lithium-ion batteries. J Electrochem Soc 149:A675

  13. 13.

    Yu P, Ritter JA, White RE, Popov BN (2000) Ni-composite microencapsulated graphite as the negative electrode in lithium-ion batteries I. Initial irreversible capacity study. J Electrochem Soc 147:1280

  14. 14.

    Shi Q, Liu W, Qu Q, Gao T, Wang Y, Liu G, Battaglia VS, Zheng H (2017) Robust solid/electrolyte interphase on graphite anode to suppress lithium inventory loss in lithium-ion batteries. Carbon 111:291

  15. 15.

    Guk H, Kim D, Choi S-H, Chung DH, Han SS (2016) Thermostable artificial solid-electrolyte interface layer covalently linked to graphite for lithium ion battery: molecular dynamics simulations. J Electrochem Soc 163:A917

  16. 16.

    Kottegoda RM, Kadoma Y, Ikuta H, Uchimoto Y, Wakiharaz M (2002) Enhancement of rate capability in graphite anode by surface modification with zirconia. Electrochem Solid State Lett 5:A275

  17. 17.

    Zhu Z, Chen X (2017) Artificial interphase engineering of electrode materials to improve the overall performance of lithium-ion batteries. Nano Res 10:4115

  18. 18.

    Jung YS, Cavanagh AS, Riley LA, Kang SH, Dillon AC, Groner MD, George SM, Lee SH (2010) Ultrathin direct atomic layer deposition on composite electrodes for highly durable and safe li-ion batteries. Adv Mater 22:2172

  19. 19.

    Wang HY, Wang FM (2013) Electrochemical investigation of an artificial solid electrolyte interface for improving the cycle-ability of lithium ion batteries using an atomic layer deposition on a graphite electrode. J Power Sources 233:1

  20. 20.

    Li X, Meng X, Liu J, Geng D, Zhang Y, Norouzi Banis M, Li Y, Yang J, Li R, Sun X, Cai M, Verbrugge MW (2012) Tin oxide with controlled morphology and crystallinity by atomic layer deposition onto graphene nanosheets for enhanced lithium storage. Adv Func Mater 22:1647

  21. 21.

    Meng X, Yang X-Q, Sun X (2012) Emerging applications of atomic layer deposition for lithium-ion battery studies. Adv Mater 24:3589

  22. 22.

    Zhang W-M, Wu XL, Hu JS, Guo YG, Wan LJ (2008) Carbon coated Fe3O4 nanospindles as a superior anode material for lithium-ion batteries. Adv Funct Mater 18:3941

  23. 23.

    Liu Y, Xie K, Pan YK, Li Y, Wang H, Lu W, Zheng C (2017) LiPON as a protective layer on graphite anode to extend the storage life of Li-ion battery at elevated temperature. Ionics 24:1–12

  24. 24.

    Ito S, Nakaoka K, Kawamura M, Ui K, Fujimoto K, Koura N (2005) Lithium battery having a large capacity using Fe3O4 as a cathode material. J Power Sources 146:319

  25. 25.

    Mitra S, Poizot P, Finke A, Tarascon JM (2006) Growth and electrochemical characterization versus lithium of Fe3O4 electrodes made by electrodeposition. Adv Funct Mater 16:2281

  26. 26.

    Taberna PL, Mitra S, Poizot P, Simon P, Tarascon JM (2006) High rate capabilities Fe3O4-based Cu nano-architectured electrodes for lithium-ion battery applications. Nat Mater 5:567

  27. 27.

    Chen JS, Zhang Y, Lou XW (2011) One-pot synthesis of uniform Fe3O4 nanospheres with carbon matrix support for improved lithium storage capabilities. ACS Appl Mater Interfaces 3:3276

  28. 28.

    Dong YC, Ma RG, Jun Hu M, Cheng H, Tsang CK, Yang QD, Yang Li Y, Zapien JA (2013) Scalable synthesis of Fe3O4 nanoparticles anchored on graphene as a high-performance anode for lithium ion batteries. J Solid State Chem 201:330

  29. 29.

    Jin B, Liu AH, Liu GY, Yang ZZ, Zhong XB, Ma XZ, Yang M, Wang HY (2012) Fe3O4-pyrolytic graphite oxide composite as an anode material for lithium secondary batteries. Electrochem Acta 90:426

  30. 30.

    Zhang L, Wu HB, David-Lou XW (2014) Iron-oxide-based advanced anode materials for lithium-ion batteries. Adv Energy Mater 4:1300958

  31. 31.

    Fei H, Peng Z, Li L, Yang Y, Lu W, Samuel ELG, Fan X, Tour JM (2014) Preparation of carbon-coated iron oxide nanoparticles dispersed on graphene sheets and applications as advanced anode materials for lithium-ion batteries. Nano Res 7:502

  32. 32.

    Tang J, Myers M, Bosnick KA, Brus LE (2003) Magnetite Fe3O4 nanocrystals: spectroscopic observation of aqueous oxidation kinetics. J Phys Chem B 107:7501

  33. 33.

    Li J, Dahn H, Krause L, Le DB, Dahn J (2008) Impact of binder choice on the performance of α-Fe2O3 as a negative electrode. J Electrochem Soc 155:A812

  34. 34.

    Winter M, Novák P, Monnier A (1998) Graphite for lithium-ion cells: the correlation of the first-cycle charge loss with the Brunauer-Emmett-Teller surface area. J Electrochem Soc 145:428

  35. 35.

    Yu P, Haran BS, Ritter JA, White RE, Popov BN (2000) Palladium-microencapsulated graphite as the negative electrode in Li-ion cells. J Power Sources 91:107

  36. 36.

    He C, Wu S, Zhao N, Shi C, Liu E, Li J (2013) Carbon-encapsulated Fe3O4 nanoparticles as a high-rate lithium ion battery anode material. ACS Nano 7:4459

  37. 37.

    Zhou G, Wang DW, Li F, Zhang L, Li N, Wu ZS, Wen L, Lu GQ, Cheng HM (2010) Graphene-wrapped Fe3O4 anode material with improved reversible capacity and cyclic stability for lithium ion batteries. Chem Mater 22:5306

  38. 38.

    Shu-he L, Zhe Y, Zuo-ming W, Feng L, Shuo B, Lei W, Hui-ming C (2008) Improving the electrochemical properties of natural graphite spheres by coating with a pyrolytic carbon shell. New Carbon Mater 23:30

  39. 39.

    Zhang HL, Liu SH, Li F, Bai S, Liu C, Tan J, Cheng HM (2006) Electrochemical performance of pyrolytic carbon-coated natural graphite spheres. Carbon 44:2212

  40. 40.

    Yu P, Ritter JA, White RE, Popov BN (2000) Ni-composite microencapsulated graphite as the negative electrode in lithium-ion batteries II: electrochemical impedance and self-discharge studies. J Electrochem Soc 147:2081

  41. 41.

    Han F, Li D, Li WC, Lei C, Sun Q, Lu AH (2013) Nanoengineered polypyrrole-coated Fe2O3@C multifunctional composites with an improved cycle stability as lithium-ion anodes. Adv Funct Mater 23:1692

Download references


Financial support from Chemical and Biomolecular Engineering department and the Center for Electrochemical Research (CEER) at Ohio University is greatly appreciated.

Author information

Correspondence to Gerardine G. Botte.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 515 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Moradi, B., Wang, D. & Botte, G.G. Carbon-coated Fe3O4 nanospindles as solid electrolyte interface for improving graphite anodes in lithium ion batteries. J Appl Electrochem 50, 321–331 (2020).

Download citation


  • Lithium ion batteries
  • Graphite recycling
  • Surface modification
  • Solid electrolyte interface
  • Capacity fade
  • Nanospindles