Journal of Materials Science

, Volume 51, Issue 1, pp 589–602 | Cite as

TEM in situ lithiation of tin nanoneedles for battery applications

  • Matthew T. Janish
  • David T. Mackay
  • Yang Liu
  • Katherine L. Jungjohann
  • C. Barry Carter
  • M. Grant Norton
50th Anniversary


Materials such as tin (Sn) and silicon that alloy with lithium (Li) have attracted renewed interest as anode materials in Li-ion batteries. Although their superior capacity to graphite and other intercalation materials has been known for decades, their mechanical instability due to extreme volume changes during cycling has traditionally limited their commercial viability. This limitation is changing as processes emerge that produce nanostructured electrodes. The nanostructures can accommodate the repeated expansion and contraction as Li is inserted and removed without failing mechanically. Recently, one such nano-manufacturing process, which is capable of depositing coatings of Sn “nanoneedles” at low temperature with no template and at industrial scales, has been described. The present work is concerned with observations of the lithiation and delithiation behavior of these Sn nanoneedles during in situ experiments in the transmission electron microscope, along with a brief review of how in situ TEM experiments have been used to study the lithiation of Li-alloying materials. Individual needles are successfully lithiated and delithiated in solid-state half-cells against a Li-metal counter-electrode. The microstructural evolution of the needles is discussed, including the transformation of one needle from single-crystal Sn to polycrystalline Sn–Li and back to single-crystal Sn.


  1. 1.
    Gyuk I, Johnson M, Vetrano J, Lynn K, Parks W, Handa R, Kannberg L, Hearne S, Waldrip K, Braccio R (2013) Grid energy storage. US Department of Energy. Accessed 9 Apr 2014
  2. 2.
    Armand M, Tarascon JM (2008) Building better batteries. Nature 451:652–657CrossRefGoogle Scholar
  3. 3.
    Goodenough JB, Kim Y, Mater C (2009) Challenges for rechargeable Li batteries. Chem Mater 22:587–603CrossRefGoogle Scholar
  4. 4.
    Wu H, Chan G, Choi JW, Ryu I, Yao Y, McDowell MT, Lee SW, Jackson A, Yang Y, Hu L, Cui Y (2012) Stable cycling of double-walled silicon nanotube battery anodes through solid- electrolyte interphase control. Nat Nanotechnol 7:310–315CrossRefGoogle Scholar
  5. 5.
    Tarascon JM, Armand M (2001) Issues and challenges facing rechargeable lithium batteries. Nature 414:359–367CrossRefGoogle Scholar
  6. 6.
    Kang B, Ceder G (2009) Battery materials for ultrafast charging and discharging. Nature 458:190–193CrossRefGoogle Scholar
  7. 7.
    Whittingham MS (2004) Lithium batteries and cathode materials. Chem Rev 104:4271–4301CrossRefGoogle Scholar
  8. 8.
    Poizot P, Laruelle S, Grugeon S, Dupont L, Tarascon JM (2000) Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries. Nature 407:496–499CrossRefGoogle Scholar
  9. 9.
    Denholm P, Jorgenson J, Hummon M, Jenkin T, Palchak D, Kirby B, Ma O, O’Malley M (2013) The value of energy storage for grid applications, edited. NREL, GoldenGoogle Scholar
  10. 10.
    Shao MH (2014) In situ microscopic studies on the structural and chemical behaviors of lithium-ion battery materials. J Power Sources 270:475–498CrossRefGoogle Scholar
  11. 11.
    Huang JY, Zhong L, Wang CM, Sullivan JP, Xu W, Zhang LO, Mao SX, Hudak NS, Liu XH, Subramanian A, Fan H, Qi L, Kushima A, Li J (2010) In situ observation of the electrochemical lithiation of a Single SnO2 nanowire electrode. Science 330:1515–1520CrossRefGoogle Scholar
  12. 12.
    Huggins RA (1998) Lithium alloy negative electrodes formed from convertible oxides. Solid State Ion 113–115:57–67CrossRefGoogle Scholar
  13. 13.
    Huggins RA (1999) Lithium alloy negative electrodes. J Power Sources 81–82:13–19CrossRefGoogle Scholar
  14. 14.
    Wang J, Raistrick ID, Huggins RA (1986) Behavior of some binary lithium alloys as negative electrodes in organic solvent-based electrolytes. J Electrochem Soc 133:457–460CrossRefGoogle Scholar
  15. 15.
    Kamili AR, Fray DJ (2011) Tin-based materials as advanced anode materials for lithium ion batteries. Rev Adv Mater Sci 27:14–24Google Scholar
  16. 16.
    Wang H, Huang H, Chen L, Wang C, Yan B, Yu Y, Yang Y, Yang G (2014) Preparation of Si/Sn-based nanoparticles composited with carbon fibers and improved electrochemical performance as anode materials. ACS Sustain Chem Eng 2:2310–2317CrossRefGoogle Scholar
  17. 17.
    Wang CM (2015) In situ transmission electron microscopy and spectroscopy studies of rechargeable batteries under dynamic operating conditions: a retrospective and perspective view. J Mater Res 30:326–339CrossRefGoogle Scholar
  18. 18.
    Park C-M, Kim J-H, Kim H, Sohn H-J (2010) Li-alloy based anode materials for Li secondary batteries. Chem Soc Rev 39:3115–3141CrossRefGoogle Scholar
  19. 19.
    Park M, Sun H, Lee H, Lee J, Cho J (2012) Lithium-air batteries: survey on the current status and perspectives towards automotive applications from a battery industry standpoint. Adv Energy Mater 2:780–800CrossRefGoogle Scholar
  20. 20.
    Egashira M, Takatsuji H, Okada S, Yamaki J (2002) Properties of containing Sn nanoparticles activated carbon fiber for a negative electrode in lithium batteries. J Power Sources 107:56–60CrossRefGoogle Scholar
  21. 21.
    Norton MG, Sahaym U (2012) Lithium-ion batteries with nanostructured electrodes and associated methods of making. US PatentGoogle Scholar
  22. 22.
    Liu XH, Zhong L, Mao SX, Zhu T, Huang JY (2012) Size-dependent fracture of silicon nanoparticles during lithiation. ACS Nano 6:1522–1531CrossRefGoogle Scholar
  23. 23.
    Liang W, Yang H, Fan F, Liu Y, Liu XH, Huang JY, Zhu T, Zhang S (2013) Tough germanium nanoparticles under electrochemical cycling. ACS Nano 7:3427–3433CrossRefGoogle Scholar
  24. 24.
    Wei Z, Mao H, Huang T, Ai Yu (2013) Facile synthesis of Sn/TiO2 nanowire array composites as superior lithium-ion battery anodes. J Power Sources 223:50–55CrossRefGoogle Scholar
  25. 25.
    Liu XH, Zhang LQ, Zhong L, Liu Y, Zheng H, Wang JW, Cho JH, Dayeh SA, Picraux ST, Sullivan JP, Mao SX, Ye ZZ, Huang JY (2011) Ultrafast electrochemical lithiation of individual Si nanowire anodes. Nano Lett 11:2251–2258CrossRefGoogle Scholar
  26. 26.
    Bogart TD, Oka D, Lu X, Gu M, Wang C, Korgel BA (2014) Lithium ion battery performance of silicon nanowires with carbon skin. ACS Nano 8:915–922CrossRefGoogle Scholar
  27. 27.
    McDowell MT, Lee SW, Harris JT, Korgel BA, Wang C, Nix WD, Cui Y (2013) In situ TEM of two-phase lithiation of amorphous silicon nanospheres. Nano Lett 13:758–764CrossRefGoogle Scholar
  28. 28.
    Gu M, Li Y, Li X, Hu S, Zhang X, Xu W, Thevuthasan S, Baer DR, Zhang JG, Liu J, Wang C (2012) In situ TEM study of lithiation behavior of silicon nanoparticles attached to and embedded in a carbon matrix. ACS Nano 6:8439–8447CrossRefGoogle Scholar
  29. 29.
    Luo L, Wu J, Luo J, Huang J, Dravid VP (2014) Dynamics of electrochemical lithiation/delithiation of graphene- encapsulated silicon nanoparticles studied by in situ TEM. Sci Rep 4:1–6Google Scholar
  30. 30.
    Wang W, Xiao Y, Wang X, Liu B, Cao M (2014) In situ encapsulation of germanium clusters in carbon nanofibers: high-performance anodes for lithium-ion batteries. ChemSusChem 7:2914–2922CrossRefGoogle Scholar
  31. 31.
    Liu XH, Huang S, Picraux ST, Li J, Zhu T, Huang JY (2011) Reversible nanopore formation in Ge nanowires during lithiation-delithiation cycling: an in situ transmission electron microscopy study. Nano Lett 11:3991–3997CrossRefGoogle Scholar
  32. 32.
    Liu Y, Liu XH, Nguyen BM, Yoo J, Sullivan JP, Picraux ST, Huang JY, Dayeh SA (2013) Tailoring lithiation behavior by interface and bandgap engineering at the nanoscale. Nano Lett 13:4876–4883CrossRefGoogle Scholar
  33. 33.
    Zhong Y, Li X, Zhang Y, Li R, Cai M, Sun X (2015) Nanostructured core–shell Sn nanowires @ CNTs with controllable thickness of CNT shells for lithium ion battery. Appl Surf Sci 332:192–197CrossRefGoogle Scholar
  34. 34.
    Hou H, Tang X, Guo M, Shi Y, Dou P, Xu X (2014) Facile preparation of Sn hollow nanospheres anodes for lithium-ion batteries by galvanic replacement. Mater Lett 128:408–411CrossRefGoogle Scholar
  35. 35.
    Wang B, Luo B, Li X, Zhi L (2012) The dimensionality of Sn anodes in Li-ion batteries. Mater Today 15:544–552CrossRefGoogle Scholar
  36. 36.
    Sides CR, Li N, Patrissi CJ, Scrosati B, Martin CR (2002) Nanoscale materials for lithium-ion batteries. MRS Bull 27:604–607CrossRefGoogle Scholar
  37. 37.
    Bai XJ, Wang B, Wang HP, Jiang JM (2015) Preparation and electrochemical properties of profiled carbon fiber-supported Sn anodes for lithium-ion batteries. J Alloy Compd 628:407–412CrossRefGoogle Scholar
  38. 38.
    Shen Z, Hu Y, Chen Y, Zhang XW, Wang K, Chen R (2015) Tin nanoparticle-loaded porous carbon nanofiber composite anodes for high current lithium-ion batteries. J Power Sources 278:660–667CrossRefGoogle Scholar
  39. 39.
    Xie J, Zheng Y, Liu S, Cao G, Zhao X (2012) One-pot in situ synthesis of Sn/carbon-fibers nanocomposite by chemical vapor deposition and its Li-storage properties. J Mater Sci Technol 28:275–279CrossRefGoogle Scholar
  40. 40.
    Yu Y, Gu L, Zhu CB, van Aken PA, Maier J (2009) Tin nanoparticles encapsulated in porous multichannel carbon microtubes: preparation by single-nozzle electrospinning and application as anode material for high-performance Li-based batteries. J Am Chem Soc 131:15984–15985CrossRefGoogle Scholar
  41. 41.
    Li Q, Wang P, Feng Q, Mao M, Liu J, Wang H, Mao SX, Zhang X-X (2014) Superior flexibility of a wrinkled carbon shell under electrochemical cycling. J Mater Chem A 2:4192CrossRefGoogle Scholar
  42. 42.
    Cui C, Liu XH, Wu N, Sun Y (2015) Facile synthesis of core/shell-structured Sn/onion-like carbon nanocapsules as high-performance anode material for lithium-ion batteries. Mater Lett 143:35–37CrossRefGoogle Scholar
  43. 43.
    Li W, Yang R, Zheng J, Li X (2013) Tandem plasma reactions for Sn/C composites with tunable structure and high reversible lithium storage capacity. Nano Energy 2:1314–1321CrossRefGoogle Scholar
  44. 44.
    Xia X, Wang X, Zhou HM, Niu X, Xue LG, Zhang XW, Wei QF (2014) The effects of electrospinning parameters on coaxial Sn/C nanofibers: morphology and lithium storage performance. Electrochim Acta 121:345–351CrossRefGoogle Scholar
  45. 45.
    Mackay DT, Janish MT, Sahaym U, Kotula PG, Jungjohann KL, Carter CB, Norton MG (2014) Template-free electrochemical synthesis of tin nanostructures. J Mater Sci 49:1476–1483. doi:10.1007/s10853-013-7917-1 CrossRefGoogle Scholar
  46. 46.
    Owen CD, Norton MG (2015) Growth mechanism of one dimensional tin nanostructures by electrodeposition. J Mater Sci. doi:10.1007/s10853-015-9323-3 Google Scholar
  47. 47.
    Janish MT, Mackay DT, Liu Y, Jungjohann KL, Carter CB, Norton MG (2014) Lithiation of tin nanoneedles investigated by in situ TEM. Microsc Microanal 19(suppl. 2):1878–1879Google Scholar
  48. 48.
    Carter CB, Janish M, Kotula PG, Roller JM, Mackay D, Huang F, Liu Y, Jungjohann KL, Cornelius C, Maric R, Norton MG (2014) TEM studies of nanomaterials and nanodevices. AMTC Lett 4:156–157Google Scholar
  49. 49.
    Janish MT, Mackay DT, Jungjohann KL, Liu Y, Carter CB, Norton MG (2014) Initial observations of the lithiation of tin nanoneedles. In: Hozák P (ed) IMC-18, Prague, p. MS-14-P-3454-3451-3452Google Scholar
  50. 50.
    Winter M, Besenhard JO (1999) Electrochemical lithiation of tin and tin-based intermetallics and composites. Electrochim Acta 45:31–50CrossRefGoogle Scholar
  51. 51.
    Wang JW, Fan FF, Liu Y, Jungjohann KL, Lee SW, Mao SX, Liu XH, Zhu T (2014) Structural evolution and pulverization of tin nanoparticles during lithiation-delithiation cycling. J Electrochem Soc 161:F3019–F3024CrossRefGoogle Scholar
  52. 52.
    Nesper R, Schnering H (1987) Li21Sn5, a Zintl phase as well as a Hume-Rothery phase. J Solid State Chem 70:48–57CrossRefGoogle Scholar
  53. 53.
    Lupu C, Mao J-G, Rabalais JW, Guloy AM, Richardson JW (2003) X-ray and neutron diffraction studies on “Li4.4Sn”. Inorg Chem 42:3765–3771CrossRefGoogle Scholar
  54. 54.
    Wagner RS, Ellis WC (1964) Vapor-liquid-solid mechanism of single crystal growth. Appl Phys Lett 4:89–90CrossRefGoogle Scholar
  55. 55.
    Schmidt V, Wittemann JV, Senz S, Gosele U (2009) Silicon nanowires: a review on aspects of their growth and their electrical properties. Adv Mater 21:2681–2702CrossRefGoogle Scholar
  56. 56.
    McIlroy DN, Zhang D, Kranov Y, Norton MG (2001) Nanosprings. Appl Phys Lett 79:1540–1542CrossRefGoogle Scholar
  57. 57.
    Panda D, Tseng TY (2013) One-dimensional ZnO nanostructures: fabrication, optoelectronic properties, and device applications. J Mater Sci 48:6849–6877. doi:10.1007/s10853-013-7541-0 CrossRefGoogle Scholar
  58. 58.
    Thabethe BS, Malgas GF, Motaung DE, Malwela T, Arendse CJ (2013) Self-catalytic growth of tin oxide nanowires by chemical vapor deposition process. J Nanomater 66:1–7CrossRefGoogle Scholar
  59. 59.
    Chan CK, Peng H, Liu G, McIlwrath K, Zhang XF, Huggins RA, Cui Y (2008) High-performance lithium battery anodes using silicon nanowires. Nat Nanotechnol 3:31–35CrossRefGoogle Scholar
  60. 60.
    Kukovitsky EF, Lvov SG, Sainov NA (2000) VLS-growth of carbon nanotubes from the vapor. Chem Phys Lett 317:65–70CrossRefGoogle Scholar
  61. 61.
    Chen CC, Bisrat Y, Luo ZP, Schaak RE, Chao CG, Lagoudas DC (2006) Fabrication of single-crystal tin nanowires by hydraulic pressure injection. J Nanotechn 17:367–374CrossRefGoogle Scholar
  62. 62.
    Djenizian T, Hanzu I, Eyraud M, Santinacci L (2008) Electrochemical fabrication of tin nanowires: A short review. C R Chimie 11:995–1003CrossRefGoogle Scholar
  63. 63.
    Zhao H, Jiang C, He X, Ren J, Wan C (2007) Advanced structures in electrodeposited tin base anodes for lithium ion batteries. Electrochim Acta 52:7820–7826CrossRefGoogle Scholar
  64. 64.
    Subramanian A, Hudak NS, Huang JY, Zhan Y, Lou J, Sullivan JP (2014) On-chip lithium cells for electrical and structural characterization of single nanowire electrodes. Nanotechnology 25:265402CrossRefGoogle Scholar
  65. 65.
    Leenheer AJ, Sullivan JP, Shaw MJ, Harris CT (2015) A sealed liquid cell for in situ transmission electron microscopy of controlled electrochemical processes. J Microelectromech. doi:10.1109/JMEMS.2014.2380771 Google Scholar
  66. 66.
    Leenheer A, Jungjohann K, Zavadil K, Sullivan J, Harris C (2015) Lithium electrodeposition dynamics in aprotic electrolyte observed in situ via transmission electron microscopy. ACS Nano 9:4379–4389CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • Matthew T. Janish
    • 1
  • David T. Mackay
    • 2
  • Yang Liu
    • 3
    • 6
  • Katherine L. Jungjohann
    • 3
  • C. Barry Carter
    • 1
    • 3
    • 4
    • 5
  • M. Grant Norton
    • 2
  1. 1.Department of Materials Science & EngineeringUniversity of ConnecticutStorrsUSA
  2. 2.School of Mechanical and Materials EngineeringWashington State UniversityPullmanUSA
  3. 3.Center for Integrated NanotechnologiesSandia National LaboratoriesAlbuquerqueUSA
  4. 4.Department of Chemical & Biomolecular EngineeringUniversity of ConnecticutStorrsUSA
  5. 5.Institute of Materials ScienceUniversity of ConnecticutStorrsUSA
  6. 6.Department of Materials Science & EngineeringNorth Carolina State UniversityRaleighUSA

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