Skip to main content
SpringerLink
Log in

Urchin-like α-MnO2 formed by nanoneedles for high-performance lithium batteries

  • Original Paper
  • Published:
Ionics Aims and scope Submit manuscript

Abstract

MnO2 nanoneedles (NNs) were synthesized by sol-gel assisted by a redox reaction between ascorbic acid and KMnO4. X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), Raman, far-infrared spectroscopy, and magnetic measurements confirm the tunnel structure of the tetragonal α-MnO2 phase. The MnO2 NNs prepared by sol-gel at moderate temperature (T ≈ 350 °C) aggregate with an urchin-like morphology observed by scanning electron (SEM) and high-resolution transmission electron (TEM) microscopy. Electrochemical investigations show an outstanding initial specific capacity ca. 230 mAh g−1 and 45 % capacity retention at 100th cycle was obtained for these MnO2 nanoneedles.

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
Fig. 8

Similar content being viewed by others

References

  1. Wei W, Cui X, Chen W, Ivey DG (2011) Manganese oxide-based materials as electrochemical supercapacitor electrodes. Chem Soc Rev 40:1697–1721

    Article  CAS  Google Scholar 

  2. Minakshi M, Nallathamby K, Mitchell DRG (2009) Electrochemical characterization of an aqueous lithium rechargeable battery: the effect of CeO2 additions to the MnO2 cathode. J Alloys Compd 479:87–90

    Article  CAS  Google Scholar 

  3. Song K, Jung J, Heo YU, Lee YC, Cho K, Kang YM (2013) α-MnO2 nanowire catalysts with ultra-high capacity and extremely low overpotential in lithium-air batteries through tailored surface arrangement. Phys Chem Chem Phys 15:20075–20079

    Article  CAS  Google Scholar 

  4. Ding YS, Shen XF, Sithambaram S, Gomez S, Kumar R, Crisostomo VMB, Suib SL, Aindow M (2005) Synthesis and catalytic activity of cryptomelane-type manganese dioxide nanomaterials produced by a novel solvent-free method. Chem Mater 17:5382–5389

    Article  CAS  Google Scholar 

  5. DeGuzman RN, Awaluddin A, Shen YF, Tian ZR, Suib SL, Ching S, O’Young CL (1995) Electrical resistivity measurements on manganese oxides with layer and tunnel structures: birnessites, todorokites and cryptomelanes. Chem Mater 7:1286–1292

    Article  CAS  Google Scholar 

  6. Solomon B, Wu J, Thomsen E, Yang J, Zhou XD (2012) Defect chemistry and transport properties in MnO2 nanowires. ECS PRIME Conf Honolulu, Abstract MA2012-02 1960

  7. Jin L, LP X, Morein C, Chen CH, Lai M, Dharmarathna S, Dobley A, Suib SL (2010) Adv Funct Mater 20:3373–3382

    Article  CAS  Google Scholar 

  8. Li JX, Wang N, Zhao Y, Ding YH, Guan LH (2011) Electrochem Commun 13:698–700

    Article  CAS  Google Scholar 

  9. Cao Y, Wei Z, He J, Zang J, Zhang Q, Zheng M, Dong Q (2012) Energy Environ Sci 5:9765–9768

    Article  CAS  Google Scholar 

  10. Jiang H, Zhao T, Ma J, Yan C, Li CZ (2011) Ultrafine manganese dioxide nanowire network for high performance supercapacitors. Chem Commun 47:1264–1266

    Article  CAS  Google Scholar 

  11. Zhang JT, Chu W, Jiang JW, Zhao XS (2011) Synthesis characterization and capacitive performance of hydrous manganese dioxide nanostructures. Nanotechnology 12:125703

    Article  Google Scholar 

  12. Chen Y, Hong Y, Ma Y, Li J (2010) Synthesis and formation mechanism of urchin-like nano/micro hybrid α-MnO2. J Alloys Compd 490:331–335

    Article  CAS  Google Scholar 

  13. Huang M, Li F, Dong F, Zhang YX, Zhang LL (2015) MnO2-based nanostructures for high-performance supercapacitors. J Mater Chem A 3:21380–21423

    Article  CAS  Google Scholar 

  14. Wu C, Xie Y, Wang D, Yang J, Li T (2003) Selected-control hydrothermal synthesis ofγ-MnO2 3D nanostructures. J Phys Chem B 107:13583–13587

    Article  CAS  Google Scholar 

  15. Subramanian V, Zhu H, Vajtai R, Ajayan PM, Wei B (2005) Hydrothermal synthesis and pseudocapacitance properties of MnO2 nanostructures. J Phys Chem B 109:20207–20214

    Article  CAS  Google Scholar 

  16. Li B, Rong G, Xie Y, Huang L, Feng C (2006) Low-temperature synthesis of α-MnO2 hollow urchins and their application in rechargeable Li+ batteries. Inorg Chem 45:6404

    Article  CAS  Google Scholar 

  17. Li WN, Yuan J, Shen XF, Gomez-Mower S, Xu LP, Sithambaram S, Aindow M, Suib SL (2006) Hydrothermal synthesis of structure- and shape-controlled manganese oxide octahedral molecular sieve nanomaterials. Adv Funct Mater 16:1247–1253

    Article  CAS  Google Scholar 

  18. Zhang Z, Mu J (2007) Hydrothermal synthesis of γ-MnOOH nanowires and α-MnO2 sea urchin-like clusters. Solid State Commun 141:427–430

    Article  CAS  Google Scholar 

  19. Xu M, Kong L, Zhou W, Li H (2007) Hydrothermal synthesis and pseudocapacitance properties of α-MnO2 hollow spheres and hollow urchins. J Phys Chem C 111:19141–19147

    Article  CAS  Google Scholar 

  20. Song XC, Zhao Y, Zheng YF (2007) Synthesis of MnO2 nanostructures with sea urchin shapes by a sodium dodecyl sulfate-assisted hydrothermal process. Cryst Growth Des 7:159–162

    Article  CAS  Google Scholar 

  21. Ni J, Lu W, Zhang L, Yue B, Shang X, Lv Y (2009) Low-temperature synthesis of monodisperse 3D manganese oxide nanoflowers and their pseudocapacitance properties. J Phys Chem C 113:54–60

    Article  CAS  Google Scholar 

  22. Tang N, Tian X, Yang C, Pi Z (2009) Facile synthesis of α-MnO2 nanostructures for supercapacitors. Mater Res Bull 44:2062–2067

    Article  CAS  Google Scholar 

  23. Yu P, Zhang X, Wang D, Wang L, Ma Y (2009) Shape-controlled synthesis of 3D hierarchical MnO2 nanostrucvtures for electrochemical supercapacitors. Cryst Growth Des 9:528–533

    Article  CAS  Google Scholar 

  24. Zeng JH, Wang YF, Yang Y, Zhang J (2010) Synthesis of sea-urchin shaped γ-MnO2 nanostructures and their application in lithium batteries. J Mater Chem 20:10915–10918

    Article  CAS  Google Scholar 

  25. He X, Yang M, Ni P, Li Y, Liu ZH (2010) Rapid synthesis of hollow structured MnO2 microspheres and their capacitance. Colloids Surf A Physicochem Eng Asp 363:64–70

    Article  CAS  Google Scholar 

  26. Wang Y, Liu H, Bao M, Li B, Su H, Wen Y, Wang F (2011) Structural-controlled synthesis of manganese oxide nanostructures and their electrochemical properties. J Alloys Compd 509:8306–8312

    Article  CAS  Google Scholar 

  27. Zhou M, Zhang X, Wang L, Wei J, Wang L, Zhu K, Feng B (2011) Growth process and microwave absorption properties of nanostructured γ-MnO2 urchins. Mater Chem Phys 130:1191–1194

    Article  CAS  Google Scholar 

  28. Zhou M, Zhang X, Wei J, Zhao S, Wang L, Feng B (2011) Morphology-controlled synthesis and novel microwave absorption properties of hollow urchinlike α-MnO2 nanostructures. J Phys Chem C 115:1398–1402

    Article  CAS  Google Scholar 

  29. Wang M, Tan W, Feng X, Koopal LK, Liu M, Liu F (2012) One-step synthesis of sea urchin-like α-MnO2 using KIO4 as the oxidant and its oxidation of arsenite. Mater Lett 77:60–62

    Article  CAS  Google Scholar 

  30. Yang W, Gao Z, Wang J, Wang B, Liu Q, Li Z, Mann T, Yang P, Zhang M, Liu L (2012) Synthesis of reduced graphene nanosheet/urchin-like manganese dioxide composite and high performance as supercapacitor electrode. Electrochim Acta 69:112–119

    Article  CAS  Google Scholar 

  31. Jung KN, Riaz A, Lee SB, Lim TH, Park SJ, Song RH, Yoon S, Shin KH, Lee JW (2013) Urchin-like α-MnO2 decorated with Au and Pd as a bi-functional catalyst for rechargeable lithium-oxygen batteries. J Power Sources 244:328–335

    Article  CAS  Google Scholar 

  32. Ma J, Cheng Q, Pavlinek V, Saha P, Li C (2013) Morphology-controllable synthesis of MnO2 hollow nanospheres and their supercapacitive performance. New J Chem 37:722–728

    Article  CAS  Google Scholar 

  33. Benhaddad L, Bazin C, Makhloufi L, Messaoudi B, Pillier F, Rahmouni K, Takenouti H (2014) Effect of synthesis duration on the morphological and structural modification of the sea urchin-nanostructured γ-MnO2 and study of its electrochemical reactivity in alkaline medium. J Solid State Electrochem 18:2111–2121

    Article  CAS  Google Scholar 

  34. Feng L, Xuan Z, Zhao H, Bai Y, Guo J, Su CW, Chen X (2014) MnO2 prepared by hydrothermal method and electrochemical performance as anode for lithium-ion battery. Nanoscale Res Lett 9:290

    Article  Google Scholar 

  35. Zhao S, Liu T, Shi D, Zhang Y, Zeng W, Li T, Miao B (2015) Hydrothermal synthesis of urchin-like MnO2 nanostructures and its electrochemical character for supercapacitor. Appl Surf Sci 351:862–868

    Article  CAS  Google Scholar 

  36. Zhang JH, Feng JY, Zhu T, Liu ZL, Li QY, Chen SZ, Xu CW (2016) Pd-doped urchin-like MnO2-carbon sphere three-dimensional (3D) material for oxygen evolution reaction. Electrochim Acta 196:661–669

    Article  CAS  Google Scholar 

  37. He W, Yang W, Wang C, Deng X, Liu B, Xu X (2016) Morphology-controlled syntheses of α-MnO2 for electrochemical energy storage. Phys Chem Chem Phys 18:15235–15243

    Article  CAS  Google Scholar 

  38. Feng L, Wang R, Shi Y, Wang H, Yang J, Zhu J, Chen Y, Yuan N (2016) Electrochemical study of hydrogen peroxide detection on MnO2 micromaterials. Int J Electrochem Sci 11:5962–5972

    Article  CAS  Google Scholar 

  39. Kharisov BI, Kharissova OV, Ortiz-Mendez U Handbook of Less-Common nanostructures, chap 8. CRC Press, Boca Raton, pp. pp. 262–pp. 283

  40. Yang JB, Zhou XD, James WJ, Malik SK, Wang CS (2004) Growth and magnetic properties of MnO2-δ nanowire microspheres. Appl Phys Lett 85:3160–3162

    Article  CAS  Google Scholar 

  41. Kim SH, Kim SJ, Oh SM (1999) Preparation of layered MnO2 via thermal decomposition of KMnO4 and its electrochemical characterizations. Chem Mater 11:557–563

    Article  CAS  Google Scholar 

  42. Witzemann EJ (1915) A new method of preparation and some interesting transformations of colloidal manganese dioxide. J Am Chem Soc 37:1079–1091

    Article  CAS  Google Scholar 

  43. Ching S, Landrigan JA, Jorgensen ML, Duan N, Suib SL, O’Young CL (1995) Sol-gel synthesis of birnessite from KMnO4 and simple sugars. Chem Mater 7:1604–1606

    Article  CAS  Google Scholar 

  44. Bach S, Henry M, Baffier N, Livage J (1990) Sol-gel synthesis of manganese oxides. J Solid State Chem 88:325–333

    Article  CAS  Google Scholar 

  45. Hashemzadeh F, Motlagh MK, Maghsoudipour A (2009) A comparative study of hydrothermal and sol-gel methods in the synthesis of MnO2 nanostructures. J Sol-Gel Technol 51:169–174

    Article  CAS  Google Scholar 

  46. Wang X, Wang X, Huang W, Sebastian PJ, Gamboa S (2005) Sol-gel template synthesis of highly ordered MnO2 nanowire arrays. J Power Sources 140:211–215

    Article  CAS  Google Scholar 

  47. Ching S, Welch EJ, Hughes SM, Bahadoor ABF, Suib SL (2002) Nonaqueous sol-gel syntheses of microporous manganese oxides. Chem Mater 14:1292–1299

    Article  CAS  Google Scholar 

  48. Ching S, Petrovay DJ, Jorgensen ML, Suib SL (1997) Sol-gel synthesis of layered birnessite-manganese oxides. Inorg Chem 36:883–890

    Article  CAS  Google Scholar 

  49. Ching S, Roark JL, Duan N, Suib SL (1997) Sol-gel route to the tunneled manganese oxide cryptomelane. Chem Mater 9:750–754

    Article  CAS  Google Scholar 

  50. Chen S, Zhu J, Han Q, Zheng Z, Yang Y, Wang X (2009) Shape-controlled synthesis of one-dimensional MnO2 via a facile quick-precipitation procedure and its electrochemical properties. Cryst Growth Des 9:4356–4361

    Article  CAS  Google Scholar 

  51. Song H, Li X, Zhang Y, Wang H, Li H, Huang J (2014) A nanocomposite of needle-like MnO2 nanowires arrays sandwiched between graphene nanosheets for supercapacitors. Ceram Int 40:1251–1255

    Article  CAS  Google Scholar 

  52. Deng D, Kim BS, Gopiraman M, Kim IS (2015) Needle-like MnO2/activated carbon nanocomposites derived from human hair as versatile electrode materials for supercapacitors. RSC Adv 5:81492–81498

    Article  CAS  Google Scholar 

  53. Liu J, Son YC, Cai J, Shen X, Suib SL, Aindow M (2004) Size control, metal substitution and catalytic application of cryptomelane nanomaterials prepared using cross-linking reagents. Chem Mater 16:276–285

    Article  CAS  Google Scholar 

  54. Portehault D, Cassaignon S, Baudrin E, Jolivet JP (2007) Morphology control of cryptomelane type MnO2 nanowires by soft chemistry, growth mechanisms in aqueous medium. Chem Mater 19:5410–5417

    Article  CAS  Google Scholar 

  55. Hashem AM, Abdel-Latif AM, Abuzeid HM, Abbas HM, Ehrenberg H, Farag RS, Mauger A, Julien CM (2011) Improvement of the electrochemical performance of nanosized α-MnO2 used as cathode material for Li-batteries by Sn-doping. J Alloys Compd 509:9669–9674

    Article  CAS  Google Scholar 

  56. Benaissa M, Jose-Yacaman M, Xiao TD, Strutt PR (1997) Microstructural study of hollandite-type MnO2 nano-fibers. Appl Phys Lett 70:2120–2122

    Article  CAS  Google Scholar 

  57. Strobel P, Darie C, Thiery F, Ibarra-Palos A, Bacia M, Proux O, Soupart JB (2006) Electrochemical lithium intercalation in nanosized manganese oxides. J Phys Chem Solids 67:1258–1264

    Article  CAS  Google Scholar 

  58. Cheng F, Zhao J, Song W, Li C, Ma H, Chen J, Shen P (2006) Facile controlled synthesis of MnO2 nanostructures of novel shapes and their application in batteries. Inorg Chem 45:2038–2044

    Article  CAS  Google Scholar 

  59. Yang Y, Xiao L, Zhao Y, Wang F (2008) Hydrothermal synthesis and electrochemical characterization of α-MnO2 nanorods as cathode material for lithium batteries. Int J Electrochem Sci 3:67–74

    CAS  Google Scholar 

  60. Li W, Cui X, Zeng R, Du G, Sun Z, Zheng R, Ringer SP, Dou SX (2015) Performance modulation of α-MnO2 nanowires by crystal facet engineering. Sci Rep 5:8987

    Article  CAS  Google Scholar 

  61. Yuan Y, Nie A, Odegard CM, Xu R, Zhou D, Santhanogopalan S, He K, Asayesh-Ardakani H, Meng DD, Klie RF, Johnson C, Lu J, Shahbazian-Yassar R (2015) Asynchronous crystal cell expansion during lithiation of K+-stabilized α-MnO2. Nano Lett 15:2998–3007

    Article  CAS  Google Scholar 

  62. Yuan Y, Wood SM, He K, Yao W, Tompsett D, Lu J, Nie A, Islam MS, Shahbazian-Yassar R (2016) Atomistic insights into the oriented attachment of tunnel-based oxide nanostructures. ACS Nano 10:539–548

    Article  CAS  Google Scholar 

  63. Momeni K, Levitas VI, Wareen JA (2015) The strong influence of internal stresses on the nucleation of a nanosized, deeply undercooled melt at a solid-solid phase interface. Nano Lett 15:2298–3007

    Article  CAS  Google Scholar 

  64. Li L, Pan Y, Chen L, Li G (2007) One-dimensional α-MnO2 trapping chemistry of tunnel structures, structural stability and magnetic transitions. J Solid State Chem 180:2896–2904

    Article  CAS  Google Scholar 

  65. Liu B, Thomas PS, Williams RP, Donne SW (2005) Thermal characterization of chemically reduced electrolytic manganese dioxide. J Therm Anal Calorim 80:625–629

    Article  CAS  Google Scholar 

  66. Julien CM, Massot M, Poinsignon C (2004) Lattice vibrations of manganese oxides: part I. Periodic structures. Spectrochim Acta A 60:689–700

    Article  CAS  Google Scholar 

  67. Gao T, Fjellvag H, Norby P (2009) A comparison study on Raman scattering properties of α- and β-MnO2. Anal Chim Acta 648:235–239

    Article  CAS  Google Scholar 

  68. Julien CM, Ait-Salah A, Mauger A, Gendron F (2006) Magnetic properties of lithium intercalation compounds. Ionics 12:21–32

    Article  CAS  Google Scholar 

  69. Johnson CS, Dees DW, Mansuetto MF, Thackeray MM, Vissers DR, Argyriou D, Loong CK, Christensen L (1997) Structural and electrochemical studies of α-manganese dioxide (α-MnO2). J Power Sources 68:570–577

    Article  CAS  Google Scholar 

  70. Fenq BR, Kanoh H, Oei K, Tani M, Nakacho Y (1994) Synthesis of hollandite-type manganese dioxide with H+ form for lithium rechargeable battery. J Electrochem Soc 141:L135–L136

    Article  Google Scholar 

  71. Tompsett DA, Islam MS (2013) Electrochemistry of hollandite α-MnO2: Li-ion and Na-ion insertion and Li2O incorporation. Chem Mater 25:2515–2526

    Article  CAS  Google Scholar 

  72. Thackeray MM (1997) Manganese oxides for lithium batteries. Prog Solid State Chem 25:1–71

    Article  CAS  Google Scholar 

  73. Johnson CS, Thackeray MM (2001) Amonia- and lithia-doped manganese dioxide for 3 V lithium batteries. J Power Sources 97-98:437–442

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors are grateful to Dr. Björn Schwarz for his kind help in measuring the magnetic properties and Mr. René Veillette for his assistance in collecting the HRTEM images and the EDX spectrum. Financial support from the Deutsche Forschungsgemeinschaft (DFG) within the Research Collaborative Centre 595 on “Electrical Fatigue in Functional Materials” is gratefully acknowledged.

Author information

Authors and Affiliations

  1. National Research Centre, Inorganic Chemistry Department, 33 El Bohouth St., (former El Tahrir St.), Dokki-Giza, 12622, Egypt

    A. M. Hashem, A. E. Abdel-Ghany & R. El-Tawil

  2. Karlsruhe Institute of Technology (KIT), Institute for Applied Materials-Energy Storage Systems (IAM- ESS), Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany

    A. M. Hashem, A. Bhaskar, B. Hunzinger & H. Ehrenberg

  3. Pierre et Marie Curie-Paris6, Physicochimie des Electrolytes et Nanosystèmes Interfaciaux (PHENIX), Sorbonne Universités, UPMC Univ., UMR 8234, 4 place Jussieu, 75005, Paris, France

    A. E. Abdel-Ghany & C. M. Julien

  4. Sorbonne Universités, UPMC Univ. Pierre et Marie Curie-Paris6, Institut de Minéralogie et Physique de la Matière Condensée (IMPMC), 4 place Jussieu, 75752, Paris cedex 05, France

    A. Mauger

Authors
  1. A. M. Hashem
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. A. E. Abdel-Ghany
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. R. El-Tawil
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. A. Bhaskar
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. B. Hunzinger
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. H. Ehrenberg
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. A. Mauger
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. C. M. Julien
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to C. M. Julien.

Additional information

Highlights

- Urchin-like α-MnO2 formed by aggregated nanoneedles are synthesized using facile route at moderate temperature (T ≈ 350 °C).

- EDX and TG analysis, vibrational spectroscopies, and magnetic measurements confirm the (2 × 2) tunnel-tetragonal α-MnO2 structure with a small amount of K+ ions in the cavities.

- Electrochemical properties of α-MnO2 nanoneedles exhibit an initial specific capacity of 230 mAh g−1 with 45 % capacity retention at the 100th cycle.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Hashem, A.M., Abdel-Ghany, A.E., El-Tawil, R. et al. Urchin-like α-MnO2 formed by nanoneedles for high-performance lithium batteries. Ionics 22, 2263–2271 (2016). https://doi.org/10.1007/s11581-016-1771-5

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11581-016-1771-5

Keywords

Search

Navigation