Skip to main content
SpringerLink
Log in

Ultra-small Co-doped Mn3O4 nanoparticles tiled on multilayer graphene with enhanced performance for lithium ion battery anodes

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

Abstract

The synthesis of ultra-small cobalt-doped (Co-doped) Mn3O4 nanoparticles tiled on multilayer graphene (MLG) surface by one-pot hydrothermal method was reported here. MLG was obtained by the ultrasonication of expanded graphite in mixture solution of N,N-Dimethylformamide (DMF) and H2O and used without any further treatment. Co-doped Mn3O4 nanoparticles were in situ assembled onto MLG surfaces by van der Waals force between metal complex and MLG. The characterization by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy revealed that the as-prepared Co-doped Mn3O4 nanoparticles were homogeneously tiled on MLG with good crystallization and uniform size. The effects of cobalt doping content on the microstructure and electrochemical performance for the composites were studied. For Co0.45Mn2.55O4/MLG composite, a reversible capacity of 906 mAh g−1 is stably delivered at 100 mA g−1 based on the overall weight and it is maintained to 442 mAh g−1 at a high current density of 2 A g−1.

Graphic abstract

Pure and Co-doped Mn3O4 nanoparticles with uniform size were synthesized to be tiled on MLG based on van der Waals force by a one-pot hydrothermal method. The effects of cobalt doping content on the microstructure and electrochemical performance of composite were studied. Co0.45Mn2.55O4/MLG composite exhibits a high reversible capacity, cycling stability and rate capability as anode material for lithium ion battery.

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

Access this article

Log in via an institution

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

Similar content being viewed by others

References

  1. Guo L, Ding Y, Qin C, Song W, Sun S, Fang K, Li W, Du J, Wang F (2018) Anchoring Mn3O4 nanoparticles onto nitrogen-doped porous carbon spheres derived from carboxymethyl chitosan as superior anodes for lithium-ion batteries. J Alloys Compd 735:209–217

    CAS  Google Scholar 

  2. Peng HJ, Hao GX, Chu ZH, Lin J, Lin XM, Cai YP (2017) Mesoporous Mn3O4/C microspheres fabricated from MOF template as advanced lithium-ion battery anode. Cryst Growth Des 17:5881–5886

    CAS  Google Scholar 

  3. Kong J, Yee WA, Wei Y, Yang L, Ang JM, Phua SL, Wong SY, Zhou R, Dong Y, Li X, Lu X (2013) Silicon nanoparticles encapsulated in hollow graphitized carbon nanofibers for lithium ion battery anodes. Nanoscale 5:2967–2973

    CAS  PubMed  Google Scholar 

  4. Liu L, Xie F, Lyu J, Zhao T, Li T, Choi BG (2016) Tin-based anode materials with well-designed architectures for next-generation lithium-ion batteries. J Power Sources 321:11–35

    CAS  Google Scholar 

  5. Chen X, Zhao Z, Zhou Y, Shu Y, Sajjad M, Bi Q, Ren Y, Wang X, Zhou X, Liu Z (2019) MWCNTs modified α-Fe2O3 nanoparticles as anode active materials and carbon nanofiber paper as a flexible current collector for lithium-ion batteries application. J Alloys Compd 776:974–983

    CAS  Google Scholar 

  6. Qiu J, Yu M, Zhang Z, Cai X, Guo G (2019) Synthesis of Co3O4/nitrogen-doped carbon composite from metal-organic framework as anode for Li-ion battery. J Alloys Compd 775:366–371

    CAS  Google Scholar 

  7. Yin L, Gao YJ, Jeon I, Yang H, Kim JP, Jeong SY, Cho CR (2019) Rice-panicle-like γ-Fe2O3@ C nanofibers as high-rate anodes for superior lithium-ion batteries. Chem Eng J 356:60–68

    CAS  Google Scholar 

  8. Zhang W, Liu F, Li Q, Shou Q, Cheng J, Zhang L, Nelson BJ, Zhang X (2012) Transition metal oxide and graphene nanocomposites for high-performance electrochemical capacitors. Phys Chem Chem Phys 14:16331–16337

    CAS  PubMed  Google Scholar 

  9. Li L, Wang L, Zhang M, Huang Q, Chen L, Wu F (2019) High-performance lithium-ion battery anodes based on Mn3O4/nitrogen-doped porous carbon hybrid structures. J Alloys Compd 775:51–58

    CAS  Google Scholar 

  10. Bai Z, Zhang X, Zhang Y, Guo C, Tang B (2014) Facile synthesis of mesoporous Mn3O4 nanorods as a promising anode material for high performance lithium-ion batteries. J Mater Chem A 2:16755–16760

    CAS  Google Scholar 

  11. Yu D, Hou Y, Han X, Zheng X, Yu S, Chen Y, Wang X (2015) Enhanced lithium-ion storage performance from high aspect ratio Mn3O4 nanowires. Mater Lett 159:182–184

    CAS  Google Scholar 

  12. Bai Z, Fan N, Ju Z, Guo C, Qian Y, Tang B, Xiong S (2013) Facile synthesis of mesoporous Mn3O4 nanotubes and their excellent performance for lithium-ion batteries. J Mater Chem A 1:10985–10990

    CAS  Google Scholar 

  13. Zhao D, Hao Q, Xu C (2015) Facile fabrication of composited Mn3O4/Fe3O4 nanoflowers with high electrochemical performance as anode material for lithium ion batteries. Electrochim Acta 180:493–500

    CAS  Google Scholar 

  14. Jian G, Xu Y, Lai LC, Wang C, Zachariah MR (2014) Mn3O4 hollow spheres for lithium-ion batteries with high rate and capacity. J Mater Chem A 2:4627–4632

    CAS  Google Scholar 

  15. Jiang Z, Huang K, Yang D, Wang S, Zhong H, Jiang C (2017) Facile preparation of Mn3O4 hollow microspheres via reduction of pentachloropyridine and their performance in lithium-ion batteries. RSC Adv 7(14):8264–8271

    CAS  Google Scholar 

  16. Hu X, Lou X, Li C, Yang Q, Chen Q, Hu B (2018) Green and rational design of 3D layer-by-layer MnOx hierarchically mesoporous microcuboids from MOF templates for high-rate and long-life Li-Ion batteries. ACS Appl Mater Interfaces 10:14684–14697

    CAS  PubMed  Google Scholar 

  17. Gao J, Lowe MA, Abruna HD (2011) Spongelike nanosized Mn3O4 as a high-capacity anode material for rechargeable lithium batteries. Chem Mater 23:3223–3227

    CAS  Google Scholar 

  18. Shaik DPMD, Rosaiah P, Ganesh KS, Qiu Y, Hussain OM (2018) Improved electrochemical performance of Mn3O4 thin film electrodes for supercapacitors. Mater Sci Semicond Process 84:83–90

    CAS  Google Scholar 

  19. Guo J, Zhang X, Du X, Zhang F (2017) A Mn3O4 nano-wall array based binder-free cathode for high performance lithium–sulfur batteries. J Mater Chem A 5:6447–6454

    CAS  Google Scholar 

  20. Cao L, Wang R, Xu Z, Li J, Huang J, Li R, Li K (2017) Constructing MnOC bonds in Mn3O4/Super P composite for superior performance in Li-ion battery. J Electroanal Chem 798:1–8

    CAS  Google Scholar 

  21. Jiang Y, Yue JL, Guo Q, Xia Q, Zhou C, Feng T, Xu J, Xia H (2018) Highly porous Mn3O4 micro/nanocuboids with in situ coated carbon as advanced anode material for lithium-ion batteries. Small 14:1704296

    Google Scholar 

  22. Chen J, Wu X, Gong Y, Wang P, Li W, Tan Q, Chen Y (2017) Synthesis of Mn3O4/N-doped graphene hybrid and its improved electrochemical performance for lithium-ion batteries. Ceram Int 43:4655–4662

    CAS  Google Scholar 

  23. Sun W, Yu Z, Lv LP, Xu Y, Liu H, Wang G, Wang Y (2017) Mn3O4 nanosheet and GNS–Mn3O4 composite as high-performance anode materials for lithium-ion batteries. Arab J Sci Eng 42:4281–4289

    CAS  Google Scholar 

  24. Wang C, Yin L, Xiang D, Qi Y (2012) Uniform carbon layer coated Mn3O4 nanorod anodes with improved reversible capacity and cyclic stability for lithium ion batteries. ACS Appl Mater Interfaces 4:1636–1642

    CAS  PubMed  Google Scholar 

  25. Liu B, Qi L, Ye J, Wang J, Xu C (2017) Facile fabrication of graphene-encapsulated Mn3O4 octahedra cross-linked with a silver network as a high-capacity anode material for lithium ion batteries. New J Chem 41:13454–13461

    CAS  Google Scholar 

  26. Liu Z, Guo R, Li F, Zheng M, Wang B, Li T, Luo Y, Meng L (2018) Reduced graphene oxide bridged, TiO2 modified and Mn3O4 intercalated Ti3C2Tx sandwich-like nanocomposite as a high performance anode for enhanced lithium storage applications. J Alloys Compd 762:643–652

    CAS  Google Scholar 

  27. Ullah I, Xu Y, Du X, Sun X, Rehman W, Zhang Y, Jin Y (2018) Al2O3 coated Mn3O4@C composite for LIBs anode with enhanced cycling stability and rate performance. Solid State Ionics 320:226–232

    CAS  Google Scholar 

  28. Chu Y, Guo L, Xi B, Feng Z, Wu F, Lin Y, Liu J, Sun D, Feng J, Qian Y, Xiong S (2018) Embedding MnO@ Mn3O4 nanoparticles in an N-doped-carbon framework derived from Mn-organic clusters for efficient lithium storage. Adv Mater 30:1704244

    Google Scholar 

  29. Wu LL, Zhao DL, Cheng XW, Ding ZW, Hu T, Meng S (2017) Nanorod Mn3O4 anchored on graphene nanosheet as anode of lithium ion batteries with enhanced reversible capacity and cyclic performance. J Alloys Compd 728:383–390

    CAS  Google Scholar 

  30. Hao Q, Liu B, Ye J, Xu C (2017) Well encapsulated Mn3O4 octahedra in graphene nanosheets with much enhanced Li-storage performances. J Colloid Interface Sci 504:603–610

    CAS  PubMed  Google Scholar 

  31. Yan DJ, Zhu XD, Mao YC, Qiu SY, Gu LL, Feng YJ, Sun KN (2017) Hierarchically organized CNT@ TiO2@ Mn3O4 nanostructures for enhanced lithium storage performance. J Mater Chem A 5:17048–17055

    CAS  Google Scholar 

  32. Zhuang Y, Ma Z, Deng Y, Song X, Zuo X, Xiao X, Nan J (2017) Sandwich-like Mn3O4/carbon nanofragment composites with a higher capacity than commercial graphite and hierarchical voltage plateaus for lithium ion batteries. Electrochim Acta 245:448–455

    CAS  Google Scholar 

  33. Rosaiah P, Zhu J, Shaik DPMD, Hussain OM, Qiu Y, Zhao L (2017) Reduced graphene oxide/Mn3O4 nanocomposite electrodes with enhanced electrochemical performance for energy storage applications. J Electroanal Chem 794:78–85

    CAS  Google Scholar 

  34. Seong CY, Park SK, Bae Y, Yoo S, Piao Y (2017) An acid-treated reduced graphene oxide/Mn3O4 nanorod nanocomposite as an enhanced anode material for lithium ion batteries. RSC Adv 7:37502–37507

    CAS  Google Scholar 

  35. Ma Y, Fang C, Ding B, Ji G, Lee JY (2013) Fe-doped MnxOy with hierarchical porosity as a high-performance lithium-ion battery anode. Adv Mater 25:4646–4652

    CAS  PubMed  Google Scholar 

  36. Pasero D, Reeves N, West AR (2005) Co-doped Mn3O4: a possible anode material for lithium batteries. J Power Sources 141:156–158

    CAS  Google Scholar 

  37. Palmieri A, Yazdani S, Kashfi-Sadabad R, Karakalos SG, Ng B, Oliveira A, Peng X, Pettes MT, Mustain WE (2018) Improved capacity retention of metal oxide anodes in li-ion batteries: increasing intraparticle electronic conductivity through na inclusion in Mn3O4. ChemElectroChem 5:2059–2063

    CAS  Google Scholar 

  38. Palaniyandy N, Nkosi FP, Raju K, Ozoemena KI (2018) Fluorinated Mn3O4 nanospheres for lithium-ion batteries: low-cost synthesis with enhanced capacity, cyclability and charge-transport. Mater Chem Phys 209:65–75

    CAS  Google Scholar 

  39. Singh B, Arya S, Sharma A, Mahajan P, Gupta J, Singh A, Verma S, Bandhoria P, Bharti V (2019) Effect of Pd concentration on the structural, morphological and photodiode properties of TiO2 nanoparticles. J Mater Sci. https://doi.org/10.1007/s10854-019-01095-5

    Article  Google Scholar 

  40. Xu J, Wu J, Luo L, Chen X, Qin H, Dravid V, Mi S, Jia C (2015) Co3O4 nanocubes homogeneously assembled on few-layer graphene for high energy density lithium-ion batteries. J Power Sources 274:816–822

    CAS  Google Scholar 

  41. Li M, Cheng JP, Wang J, Liu F, Zhang XB (2016) The growth of nickel-manganese and cobalt-manganese layered double hydroxides on reduced graphene oxide for supercapacitor. Electrochim Acta 206:108–115

    CAS  Google Scholar 

  42. Zhang R, Wang D, Qin LC, Wen G, Pan H, Zhang Y, Tian N, Zhou Y, Huang X (2017) MnCO3/Mn3O4/reduced graphene oxide ternary anode materials for lithium-ion batteries: facile green synthesis and enhanced electrochemical performance. J Mater Chem A 5:17001–17011

    CAS  Google Scholar 

  43. Sun M, Zhang H, Wang YF, Liu WL, Ren MM, Kong FG, Wang SJ, Wang XQ, Duan XL, Ge SZ (2019) Co/CoO@ NC nanocomposites as high-performance anodes for lithium-ion batteries. J Alloys Compd 771:290–296

    CAS  Google Scholar 

  44. Nam I, Kim ND, Kim GP, Park J, Yi J (2013) One step preparation of Mn3O4/graphene composites for use as an anode in Li ion batteries. J Power Sources 244:56–62

    CAS  Google Scholar 

  45. Chen WQ, Wang J, Ma KY, Li M, Guo SH, Liu F, Cheng JP (2018) Hierarchical NiCo2O4@ Co-Fe LDH core-shell nanowire arrays for high-performance supercapacitor. Appl Surf Sci 451:280–288

    CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. College of Electronic Information, Hangzhou Dianzi University, Hangzhou, 310018, People’s Republic of China

    Linjuan Zhang, Junming Xu, Xiaoping Hu, Kaixin Song & Jun Wu

  2. Department of Chemistry, Huzhou University, Huzhou, 313000, People’s Republic of China

    Bin Li

  3. School of Materials Science & Engineering, Zhejiang University, Hangzhou, 310027, People’s Republic of China

    J. P. Cheng

Authors
  1. Linjuan Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Junming Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xiaoping Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Kaixin Song
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jun Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Bin Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. J. P. Cheng
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Junming Xu, Bin Li or J. P. Cheng.

Additional information

Publisher's Note

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

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, L., Xu, J., Hu, X. et al. Ultra-small Co-doped Mn3O4 nanoparticles tiled on multilayer graphene with enhanced performance for lithium ion battery anodes. J Appl Electrochem 49, 1193–1202 (2019). https://doi.org/10.1007/s10800-019-01358-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10800-019-01358-3

Keywords

Search

Navigation