Frontiers of Materials Science

, Volume 12, Issue 3, pp 214–224 | Cite as

CoP nanoparticles enwrapped in N-doped carbon nanotubes for high performance lithium-ion battery anodes

  • Mengna Chen
  • Peiyuan Zeng
  • Yueying Zhao
  • Zhen FangEmail author
Research Article


CoP is a candidate lithiumstorage material for its high theoretical capacity. However, large volume variations during the cycling processes haunted its application. In this work, a four-step strategy was developed to synthesize N-doped carbon nanotubes wrapping CoP nanoparticles (CoP@N-CNTs). Integration of nanosized particles and hollow-doped CNTs render the as-prepared CoP@N-CNTs excellent cycling stability with a reversible charge capacity of 648 mA·h·g−1 at 0.2 C after 100 cycles. The present strategy has potential application in the synthesis of phosphide enwrapped in carbon nanotube composites which have potential application in lithium-ion storage and energy conversion.


composites nanostructures chemical synthesis electron microscopy energy storage 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.



The present work was financially supported from the National Natural Science Foundation of China (Grant Nos. 21671005 and 21171007), the Anhui Provincial Natural Science Foundation for Distinguished Youth (1808085J27), the Programs for Science and Technology Development of Anhui Province (1501021019), and the Recruitment Program for Leading Talent Team of Anhui Province.

Supplementary material

11706_2018_426_MOESM1_ESM.pdf (204 kb)
Supplementary information


  1. [1]
    Armand M, Tarascon J M. Building better batteries. Nature, 2008, 451(7179): 652–657CrossRefGoogle Scholar
  2. [2]
    Tarascon J M, Armand M. Issues and challenges facing rechargeable lithium batteries. Nature, 2001, 414(6861): 359–367CrossRefGoogle Scholar
  3. [3]
    Du H, Yuan C, Huang K, et al. A novel gelatin-guided mesoporous bowknot-like Co3O4 anode material for high-performance lithiumion batteries. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2017, 5(11): 5342–5350CrossRefGoogle Scholar
  4. [4]
    Yang Z, Ren J, Zhang Z, et al. Recent advancement of nanostructured carbon for energy applications. Chemical Reviews, 2015, 115(11): 5159–5223CrossRefGoogle Scholar
  5. [5]
    Qiao L, Qiao L, Li X W, et al. Synthesis and lithium storage properties of interconnected fullerene-like carbon nanofibers encapsulated with tin nanoparticles. Journal of Materials Science, 2017, 52(12): 6969–6975CrossRefGoogle Scholar
  6. [6]
    Su X, Wu Q, Zhan X, et al. Advanced titania nanostructures and composites for lithium ion battery. Journal of Materials Science, 2012, 47(6): 2519–2534CrossRefGoogle Scholar
  7. [7]
    Yu J, He Y, Ge Z, et al. A promising physical method for recovery of LiCoO2 and graphite from spent lithium-ion batteries: Grinding flotation. Separation and Purification Technology, 2018, 190: 45–52CrossRefGoogle Scholar
  8. [8]
    Wang X X, Wang W W, Zhu B C, et al. Mo-doped Na3V2(PO4)3@C composites for high stable sodium ion battery cathode. Frontiers of Materials Science, 2018, 12(1): 53–63CrossRefGoogle Scholar
  9. [9]
    Zhu Y, You J, Huang H, et al. Facile synthesis and electrochemical properties of layered Li[Ni1/3Mn1/3Co1/3]O2 as cathode materialsfor lithium-ion batteries. Frontiers of Materials Science, 2017, 11 (2): 155–161CrossRefGoogle Scholar
  10. [10]
    Sun M, Liu H J, Qu J H, et al. Earth-rich transition metal phosphide for energy conversion and storage. Advanced Energy Materials, 2016, 6(13): 1600087CrossRefGoogle Scholar
  11. [11]
    Woo S G, Jung J H, Kim H, et al. Electrochemical characteristics of Ti–P composites prepared by mechanochemical synthesis. Journal of the Electrochemical Society, 2006, 153(10): A1979–A1983CrossRefGoogle Scholar
  12. [12]
    Lu Y, Tu J P, Xiong Q Q, et al. Synthesis of dinickel phosphide (Ni2P) for fast lithium-ion transportation: a new class of nanowires with exceptionally improved electrochemical performance as a negative electrode. RSC Advances, 2012, 2(8): 3430–3436CrossRefGoogle Scholar
  13. [13]
    Liu J, Kopold P, Wu C, et al. Uniform yolk–shell Sn4P3@C nanospheres as high-capacity and cycle-stable anode materials for sodium-ion batteries. Energy & Environmental Science, 2015, 8 (12): 3531–3538CrossRefGoogle Scholar
  14. [14]
    Fullenwarth J, Darwiche A, Soares A, et al. NiP3: a promising negative electrode for Li-and Na-ion batteries. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2014, 2(7): 2050–2059CrossRefGoogle Scholar
  15. [15]
    Jiang J,WangWL,Wang C D, et al. Electrochemical performance of iron diphosphide/carbon tube nanohybrids in lithium-ion batteries. Electrochimica Acta, 2015, 170: 140–145CrossRefGoogle Scholar
  16. [16]
    Wang C D, Jiang J, Zhou X L, et al. Alternative synthesis of cobalt monophosphide@C core–shell nanocables for electrochemical hydrogen production. Journal of Power Sources, 2015, 286: 464–469CrossRefGoogle Scholar
  17. [17]
    Wang N N, Bai Z C, Qian Y T, et al. One-dimensional yolk–shell Sb@Ti–O–P nanostructures as a high-capacity and high-rate anode material for sodium ion batteries. ACS Applied Materials & Interfaces, 2017, 9(1): 447–454CrossRefGoogle Scholar
  18. [18]
    Stan M C, Klopsch R, Bhaskar A, et al. Cu3P binary phosphide: synthesis via a wet mechanochemical method and electrochemical behavior as negative electrode material for lithium-ion batteries. Advanced Energy Materials, 2013, 3(2): 231–238CrossRefGoogle Scholar
  19. [19]
    Feng L, Xue H. Advances in transition-metal phosphide applications in electrochemical energy storage and catalysis. ChemElectroChem, 2017, 4(1): 20–34CrossRefGoogle Scholar
  20. [20]
    Takeuchi S, Yano S, Fukutsuka T, et al. Electrochemical intercalation/de-intercalation of lithium ions at graphite negative electrode in TMP-based electrolyte solution. Journal of the Electrochemical Society, 2012, 159(12): A2089–A2091CrossRefGoogle Scholar
  21. [21]
    Yang J, Zhang Y, Sun C, et al. Graphene and cobalt phosphide nanowire composite as an anode material for high performance lithium-ion batteries. Nano Research, 2016, 9(3): 612–621CrossRefGoogle Scholar
  22. [22]
    Ge X, Li Z, Yin L. Metal–organic frameworks derived porous core/shell CoP@C polyhedrons anchored on 3D reduced graphene oxide networks as anode for sodium-ion battery. Nano Energy, 2017, 32: 117–124CrossRefGoogle Scholar
  23. [23]
    Park M H, Cho Y, Kim K, et al. Germanium nanotubes prepared by using the Kirkendall effect as anodes for high-rate lithium batteries. Angewandte Chemie International Edition, 2011, 50 (41): 9647–9650CrossRefGoogle Scholar
  24. [24]
    Park M H, Kim K, Kim J, et al. Flexible dimensional control of high-capacity Li-ion-battery anodes: From 0D hollow to 3D porous germanium nanoparticle assemblies. Advanced Materials, 2010, 22(3): 415–418CrossRefGoogle Scholar
  25. [25]
    Gu J, Collins S M, Carim A I, et al. Template-free preparation of crystalline Ge nanowire film electrodes via an electrochemical liquid–liquid–solid process in water at ambient pressure and temperature for energy storage. Nano Letters, 2012, 12(9): 4617–4623CrossRefGoogle Scholar
  26. [26]
    Xue D J, Xin S, Yan Y, et al. Improving the electrode performance of Ge through Ge@C core–shell nanoparticles and graphene networks. Journal of the American Chemical Society, 2012, 134 (5): 2512–2515CrossRefGoogle Scholar
  27. [27]
    Guo Q, Ru Q, Wang B, et al. The electrochemical confrontation between CoP microflake and Co3O4 microsphere via a similar synthesis process as anodes for lithium ion batteries. Journal of Alloys and Compounds, 2017, 728: 910–916CrossRefGoogle Scholar
  28. [28]
    Wang B, Ru Q, Guo Q, et al. Fabrication of one-dimensional mesoporous CoP nanorods as anode materials for lithium-ion batteries. European Journal of Inorganic Chemistry, 2017, 2017 (31): 3729–3735CrossRefGoogle Scholar
  29. [29]
    Xu X, Liu J, Hu R, et al. Self-supported CoP nanorod arrays grafted on stainless steel as an advanced integrated anode for stable and long-life lithium-ion batteries. Chemistry—a European Journal, 2017, 23(22): 5198–5204CrossRefGoogle Scholar
  30. [30]
    Jiang J, Wang C, Li W, et al. One-pot synthesis of carbon-coated Ni5P4 nanoparticles and CoP nanorods for high-rate and highstability lithium-ion batteries. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2015, 3(46): 23345–23351CrossRefGoogle Scholar
  31. [31]
    Cui Y H, Xue MZ, Fu Z W, et al. Nanocrystalline CoP thin film as a new anode material for lithium ion battery. Journal of Alloys and Compounds, 2013, 555: 283–290CrossRefGoogle Scholar
  32. [32]
    Kwon H T, Kim J H, Jeon K J, et al. CoxP compounds: electrochemical conversion/partial recombination reaction and partially disproportionated nanocomposite for Li-ion battery anodes. RSC Advances, 2014, 4(81): 43227–43234CrossRefGoogle Scholar
  33. [33]
    Li W J, Yang Q R, Chou S L, et al. Cobalt phosphide as a new anode material for sodium storage. Journal of Power Sources, 2015, 294: 627–632CrossRefGoogle Scholar
  34. [34]
    Lu A, Zhang X, Chen Y, et al. Synthesis of Co2P/graphene nanocomposites and their enhanced properties as anode materialsfor lithium ion batteries. Journal of Power Sources, 2015, 295: 329–335CrossRefGoogle Scholar
  35. [35]
    Chan C K, Zhang X F, Cui Y. High capacity Li ion battery anodes using Ge nanowires. Nano Letters, 2008, 8(1): 307–309CrossRefGoogle Scholar
  36. [36]
    Seo M H, Park M, Lee K T, et al. High performance Ge nanowire anode sheathed with carbon for lithium rechargeable batteries. Energy & Environmental Science, 2011, 4(2): 425–428CrossRefGoogle Scholar
  37. [37]
    Kim H, Son Y, Park C, et al. Catalyst-free direct growth of a single to a few layers of graphene on a germanium nanowire for the anode material of a lithium battery. Angewandte Chemie International Edition, 2013, 52(23): 5997–6001CrossRefGoogle Scholar
  38. [38]
    Wang Z, Chen X, Zhang M, et al. Synthesis of Co3O4 nanorod bunches from a single precursor Co(CO3)0.35Cl0.20(OH)1.10. Solid State Sciences, 2005, 7(1): 13–15CrossRefGoogle Scholar
  39. [39]
    Bai Y, Zhang H, Feng Y, et al. Sandwich-like CoP/C nanocomposites as efficient and stable oxygen evolution catalysts. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2016, 4(23): 9072–9079CrossRefGoogle Scholar
  40. [40]
    Chang J, Xiao Y, Xiao M, et al. Surface oxidized cobalt-phosphide nanorods as an advanced oxygen evolution catalyst in alkaline solution. ACS Catalysis, 2015, 5(11): 6874–6878CrossRefGoogle Scholar
  41. [41]
    Ryu J, Jung N, Jang J H, et al. In situ transformation of hydrogenevolving CoP nanoparticles: toward efficient oxygen evolution catalysts bearing dispersed morphologies with Co-oxo/hydroxo molecular units. ACS Catalysis, 2015, 5(7): 4066–4074CrossRefGoogle Scholar
  42. [42]
    Li M, Liu X, Xiong Y, et al. Facile synthesis of various highly dispersive CoP nanocrystal embedded carbon matrices as efficient electrocatalysts for the hydrogen evolution reaction. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2015, 3(8): 4255–4265CrossRefGoogle Scholar
  43. [43]
    Ma Y Y, Wu C X, Feng X J, et al. Highly efficient hydrogen evolution from seawater by a low-cost and stable CoMoP@C electrocatalyst superior to Pt/C. Energy & Environmental Science, 2017, 10(3): 788–798CrossRefGoogle Scholar
  44. [44]
    Lopez MC, Ortiz G F, Tirado J L. A functionalized Co2P negative electrode for batteries demanding high Li-potential reaction. Journal of the Electrochemical Society, 2012, 159(8): A1253–A1261CrossRefGoogle Scholar
  45. [45]
    Lu Y, Tu J P, Xiang J Y, et al. Improved electrochemical performance of self-assembled hierarchical nanostructured nickel phosphide as a negative electrode for lithium ion batteries. The Journal of Physical Chemistry C, 2011, 115(48): 23760–23767CrossRefGoogle Scholar
  46. [46]
    Carenco S, Surcin C, Morcrette M, et al. Improving the Lielectrochemical properties of monodisperse Ni2P nanoparticles by self-generated carbon coating. Chemistry of Materials, 2012, 24 (4): 688–697CrossRefGoogle Scholar
  47. [47]
    Boyanov S, Zitoun D, Menetrier M, et al. Comparison of the electrochemical lithiation/delitiation mechanisms of FePx (x = 1, 2, 4) based electrodes in Li-ion batteries. The Journal of Physical Chemistry C, 2009, 113(51): 21441–21452CrossRefGoogle Scholar
  48. [48]
    Yang D, Zhu J, Rui X, et al. Synthesis of cobalt phosphides and their application as anodes for lithium ion batteries. ACS Applied Materials & Interfaces, 2013, 5(3): 1093–1099CrossRefGoogle Scholar
  49. [49]
    Ma Q Y, Ye M, Zeng P Y, et al. Size-controllable synthesis of amorphous GeOx hollow spheres and their lithium-storage electrochemical properties. RSC Advances, 2016, 6(19): 15952–15959CrossRefGoogle Scholar
  50. [50]
    Wen Z, Cui S, Kim H, et al. Binding Sn-based nanoparticles on graphene as the anode of rechargeable lithium-ion batteries. Journal of Materials Chemistry, 2012, 22(8): 3300–3306CrossRefGoogle Scholar
  51. [51]
    Wang Z, Wang Z, Liu W, et al. Amorphous CoSnO3@C nanoboxes with superior lithium storage capability. Energy & Environmental Science, 2013, 6(1): 87–91CrossRefGoogle Scholar
  52. [52]
    Zhou Q, Liu L, Huang Z, et al. Co3S4@polyaniline nanotubes as high-performance anode materials for sodium ion batteries. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2016, 4(15): 5505–5516CrossRefGoogle Scholar

Copyright information

© Higher Education Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Mengna Chen
    • 1
    • 2
  • Peiyuan Zeng
    • 1
    • 2
  • Yueying Zhao
    • 1
    • 2
  • Zhen Fang
    • 1
    • 2
    Email author
  1. 1.College of Chemistry and Materials ScienceAnhui Normal UniversityWuhuChina
  2. 2.Key Laboratory of Functional Molecular Solids (Ministry of Education)Anhui Normal UniversityWuhuChina

Personalised recommendations