Study on the performance of MnO2-MoO3 composite as lithium-ion battery anode using spent Zn-Mn batteries as manganese source

  • 20 Accesses


The recycling of Zn-Mn batteries was linked with the synthesis of MnO2-MoO3 composite in this paper. An intermediate product of MnSO4 was recycled from spent Zn-Mn batteries by hydrometallurgy recycling technology, and it was selected as manganese source to synthesize MnO2-MoO3 composite via a facile one-step hydrothermal method. The composition, morphology, and valence state of the final product MnO2-MoO3 are characterized by X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy. As anode for lithium-ion batteries, the obtained composite of MnO2-MoO3 on copper foil presents outstanding electrochemical performance. The composite attains an initial specific capacity of 2333.1 mAh g−1 and stays 908.8 mAh g−1 after 50 cycles at a current rate of 100 mA g−1 in the voltage range of 0.01–3.0 V, much higher than that of pure MnO2. Even at a high current rate of 500 mA g−1, the capacity still remains at 371.1 mAh g−1 after 50 cycles. Moreover, the lithiation and delithiation processes of MnO2-MoO3 anode material were investigated in detail by X-ray diffraction characterization.

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

Access options

Buy single article

Instant unlimited access to the full article PDF.

US$ 39.95

Price includes VAT for USA

Subscribe to journal

Immediate online access to all issues from 2019. Subscription will auto renew annually.

US$ 99

This is the net price. Taxes to be calculated in checkout.

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


  1. 1.

    Chen WS, Liao CT, Lin KY (2017) Recovery zinc and manganese from spent battery powder by hydrometallurgical route. Energy Procedia 107:167–174

  2. 2.

    Ebin B, Petranikova M, Steenari BM (2019) Recovery of industrial valuable metals from household battery waste. Waste Manag Res 37(2):168–175

  3. 3.

    Buzatu T, Popescu G, Birloaga I (2013) Study concerning the recovery of zinc and manganese from spent batteries by hydrometallurgical processes. Waste Manag 33(3):699–705

  4. 4.

    Cai S, Wang G, Jiang M (2017) Template-free fabrication of porous CuCo2O4 hollow spheres and their application in lithium ion batteries. J Solid State Electrochem 21(4):1129–1136

  5. 5.

    Lakshmi D, Nalini B (2017) Performance of SnSb: Ce, Co alloy as anode for lithium-ion batteries. J Solid State Electrochem 21(4):1027–1034

  6. 6.

    Croguennec L, Palacin MR (2015) Recent achievements on inorganic electrode materials for lithium-ion batteries. J Am Chem Soc 137(9):3140–3156

  7. 7.

    Zhang J, Gu J, He H (2017) High-capacity nano-Si@SiOx@C anode composites for lithium-ion batteries with good cyclic stability. J Solid State Electrochem 21(8):2259–2267

  8. 8.

    Li X, Li D, Wei Z (2014) Interconnected MnO2 nanoflakes supported by 3D nanostructured stainless steel plates for lithium ion battery anodes. Electrochim Acta 121:415–420

  9. 9.

    Xiang Z, Chen Y, Li J (2017) Submicro-sized porous SiO2/C and SiO2/C/graphene spheres for lithium ion batteries. J Solid State Electrochem 21(8):2425–2432

  10. 10.

    Zhang L, Xia G, Huang Y (2018) MnO quantum dots embedded in carbon nanotubes as excellent anode for lithium-ion batteries. Energy Storage Mater 10:160–167

  11. 11.

    Xiao J, Zhang X, Gao T (2017) Electrochemical formation of multilayered NiO film/Ni foam as a high-efficient anode for methanol electrolysis. J Solid State Electrochem 21(8):2301–2311

  12. 12.

    Cetinkaya T, Tokur M, Ozcan S (2016) Graphene supported α-MnO2 nanocomposite cathodes for lithium ion batteries. Int J Hydrog Energy 41(16):6945–6953

  13. 13.

    Mao W, Ai G, Dai Y (2016) In-situ synthesis of MnO2@CNT microsphere composites with enhanced electrochemical performances for lithium-ion batteries. J Power Sources 310:54–60

  14. 14.

    Jiang C, Wang J, Chen Z (2017) Nitrogen-doped hierarchical carbon spheres derived from MnO2-templated spherical polypyrrole as excellent high rate anode of Li-ion batteries. Electrochim Acta 245:279–286

  15. 15.

    Liu H, Hu Z, Su Y (2017) MnO2 nanorods/3D-rGO composite as high performance anode materials for Li-ion batteries. Appl Surf Sci 392:777–784

  16. 16.

    Weng SC, Brahma S, Chang CC (2017) Synthesis of MnOx/reduced graphene oxide nanocomposite as an anode electrode for lithium-ion batteries. Ceram Int 43(6):4873–4879

  17. 17.

    Ette PM, Selvakumar K, Kumar SMS (2018) Silica template assisted synthesis of ordered mesoporous β-MnO2 nanostructures and their performance evaluation as negative electrode in Li-ion batteries. Electrochim Acta 292:532–539

  18. 18.

    Cao Z, Chen X, Xing L (2018) Nano-MnO2@TiO2 microspheres: a novel structure and excellent performance as anode of lithium-ion batteries. J Power Sources 379:174–181

  19. 19.

    Wang D, Wang Y, Li Q (2018) Urchin-like α-Fe2O3/MnO2 hierarchical hollow composite microspheres as lithium-ion battery anodes. J Power Sources 393:186–192

  20. 20.

    Asif M, Rashad M, Ali Z (2018) Ni-doped MnO2/CNT nanoarchitectures as a cathode material for ultra-long life magnesium/lithium hybrid ion batteries. Mater Today Energy 10:108–117

  21. 21.

    Opra DP, Gnedenkov SV, Sokolov AA, Podgorbunsky AB, Laptash NM, Sinebryukhov SL (2015) Fluorine substituted molybdenum oxide as cathode material for Li-ion battery. Mater Lett 160:175–178

  22. 22.

    Kumar A, Prajapati CS, Sahay PP (2019) Results on the microstructural, optical and electrochromic properties of spray-deposited MoO3 thin films by the influence of W doping. Mater Sci Semicond Process 104:104668

  23. 23.

    Wang W, Qin J, Yin Z, Cao M (2016) Achieving fully reversible conversion in MoO3 for lithium ion batteries by rational introduction of CoMoO4. ACS Nano 10(11):10106–10116

  24. 24.

    Cheng X, Li Y, Sang L (2018) Boosting the electrochemical performance of MoO3 anode for long-life lithium ion batteries: dominated by an ultrathin TiO2 passivation layer. Electrochim Acta 269:241–249

  25. 25.

    Teng Y, Zhao H, Zhang Z (2019) Self-assembly of flower-like MoO3-NiO microspheres with carbon coating as high-performance anode material for lithium-ion batteries. Mater Lett 246:141–143

  26. 26.

    Cao L, Li Y, Wu J (2018) Facile synthesis of carbon coated MoO3 nanorods decorated with WO2 nanoparticles as stable anodes for lithium-ion batteries. J Alloys Compd 744:672–678

  27. 27.

    Wang Q, Zhang DA, Wang Q (2014) High electrochemical performances of α-MoO3@MnO2 core-shell nanorods as lithium-ion battery anodes. Electrochim Acta 146:411–418

  28. 28.

    Zhang W, Zhang B, Jin H (2018) Waste eggshell as bio-template to synthesize high capacity δ-MnO2 nanoplatelets anode for lithium ion battery. Ceram Int 44(16):20441–20448

  29. 29.

    Liu H, Hu Z, Tian L (2016) Reduced graphene oxide anchored with δ-MnO2 nanoscrolls as anode materials for enhanced Li-ion storage. Ceram Int 42(12):13519–13524

  30. 30.

    Zhai X, Mao Z, Zhao G (2018) Nanoflake δ-MnO2 deposited on carbon nanotubes-graphene-Ni foam scaffolds as self-standing three-dimensional porous anodes for high-rate-performance lithium-ion batteries. J Power Sources 402:373–380

  31. 31.

    Biesinger MC, Payne BP, Grosvenor AP, Lau LW, Gerson AR, Smart RSC (2011) Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni. Appl Surf Sci 257(7):2717–2730

  32. 32.

    Naresh N, Jena P, Satyanarayana N (2019) Facile synthesis of MoO3/rGO nanocomposite as anode materials for high performance lithium-ion battery applications. J Alloys Compd 810:151920

  33. 33.

    Wang S, Li Q, Pu W, Wu Y, Yang M (2016) MoO3-MnO2 intergrown nanoparticle composite prepared by one-step hydrothermal synthesis as anode for lithium ion batteries. J Alloys Compd 663:148–155

  34. 34.

    Chen J, Wang Y, He X (2014) Electrochemical properties of MnO2 nanorods as anode materials for lithium ion batteries. Electrochim Acta 142:152–156

  35. 35.

    Fang J, Yuan YF, Wang LK (2013) Synthesis and electrochemical performances of ZnO/MnO2 sea urchin-like sleeve array as anode materials for lithium-ion batteries. Electrochim Acta 112:364–370

  36. 36.

    Su Y, Zhang J, Liu K, Huang Z, Ren X, Wang CA (2017) Simple synthesis of a double-shell hollow structured MnO2@TiO2 composite as an anode material for lithium ion batteries. RSC Adv 7(73):46263–46270

  37. 37.

    Zhong N (2016) Facile synthesis of MnO2 nanoparticles well dispersed on graphene for the enhanced electrochemical performance. Int J Electrochem Sci 11:2525–2533

  38. 38.

    Wang H, Xie S, Yao T, Wang J, She Y, Shi JW, Leung MK (2019) Casting amorphorized SnO2/MoO3 hybrid into foam-like carbon nanoflakes towards high-performance pseudocapacitive lithium storage. J Colloid Interface Sci 547:299–308

  39. 39.

    Wang Y, Guo W, Yang Y (2018) Rational design of SnO2@C@MnO2 hierarchical hollow hybrid nanospheres for a Li-ion battery anode with enhanced performances. Electrochim Acta 262:1–8

  40. 40.

    Xia H, Lai M, Lu L (2010) Nanoflaky MnO2/carbon nanotube nanocomposites as anode materials for lithium-ion batteries. J Mater Chem 20(33):6896–6902

  41. 41.

    Yan DJ, Zhu XD, Gao XT (2018) Smartly designed hierarchical MnO2@Fe3O4/CNT hybrid films as binder-free anodes for superior lithium storage. Chemistry: Asian J 13(20):3027–3031

  42. 42.

    Icaza JC, Guduru RK (2017) Characterization of α-MoO3 anode with aqueous beryllium sulfate for supercapacitors. J Alloys Compd 726:453–459

  43. 43.

    Hu R, Liu T, Chen B (2018) Atomic mechanical properties of structure and diffusion in the MoO3 anode materials during lithiation. Comput Mater Sci 145:8–13

  44. 44.

    Palaniyandy N, Nkosi FP, Raju K (2019) Conversion of electrolytic MnO2 to Mn3O4 nanowires for high-performance anode materials for lithium-ion batteries. J Electroanal Chem 833:79–92

  45. 45.

    Kim H, Venugopal N, Yoon J (2019) A facile and surfactant-free synthesis of porous hollow λ-MnO2 3D nanoarchitectures for lithium ion batteries with superior performance. J Alloys Compd 778:37–46

  46. 46.

    Wang Q, Sun J, Wang Q, Zhang DA, Xing L, Xue X (2015) Electrochemical performance of α-MoO3-In2O3 core-shell nanorods as anode materials for lithium-ion batteries. J Mater Chem A 3(9):5083–5091

  47. 47.

    Xue XY, Chen ZH, Xing LL, Yuan S, Chen YJ (2011) SnO2/α-MoO3 core-shell nanobelts and their extraordinarily high reversible capacity as lithium-ion battery anodes. Chem Commun 47(18):5205–5207

  48. 48.

    Wang Q, Wang Q, Zhang DA, Sun J, Xing LL, Xue XY (2014) Core-shell α-Fe2O3@α-MoO3 nanorods as lithium-ion battery anodes with extremely high capacity and cyclability. Chemistry: Asian J 9(11):3299–3306

Download references

Author information

Correspondence to Ningsheng Zhang.

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

Verify currency and authenticity via CrossMark

Cite this article

Zhang, N., Guo, G., He, B. et al. Study on the performance of MnO2-MoO3 composite as lithium-ion battery anode using spent Zn-Mn batteries as manganese source. J Solid State Electrochem (2020) doi:10.1007/s10008-020-04496-3

Download citation


  • Recycling
  • MnO2-MoO3
  • Composite
  • Anode
  • Lithium-ion batteries