Skip to main content
SpringerLink
Log in

TEM in situ lithiation of tin nanoneedles for battery applications

  • 50th Anniversary
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

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.

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
Fig. 9

Similar content being viewed by others

References

  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. http://energy.gov/oe/downloads/grid-energy-storage-december-2013. Accessed 9 Apr 2014

  2. Armand M, Tarascon JM (2008) Building better batteries. Nature 451:652–657

    Article  Google Scholar 

  3. Goodenough JB, Kim Y, Mater C (2009) Challenges for rechargeable Li batteries. Chem Mater 22:587–603

    Article  Google Scholar 

  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 7:310–315

    Article  Google Scholar 

  5. Tarascon JM, Armand M (2001) Issues and challenges facing rechargeable lithium batteries. Nature 414:359–367

    Article  Google Scholar 

  6. Kang B, Ceder G (2009) Battery materials for ultrafast charging and discharging. Nature 458:190–193

    Article  Google Scholar 

  7. Whittingham MS (2004) Lithium batteries and cathode materials. Chem Rev 104:4271–4301

    Article  Google Scholar 

  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 407:496–499

    Article  Google Scholar 

  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, Golden

    Google Scholar 

  10. Shao MH (2014) In situ microscopic studies on the structural and chemical behaviors of lithium-ion battery materials. J Power Sources 270:475–498

    Article  Google Scholar 

  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 330:1515–1520

    Article  Google Scholar 

  12. Huggins RA (1998) Lithium alloy negative electrodes formed from convertible oxides. Solid State Ion 113–115:57–67

    Article  Google Scholar 

  13. Huggins RA (1999) Lithium alloy negative electrodes. J Power Sources 81–82:13–19

    Article  Google Scholar 

  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 133:457–460

    Article  Google Scholar 

  15. Kamili AR, Fray DJ (2011) Tin-based materials as advanced anode materials for lithium ion batteries. Rev Adv Mater Sci 27:14–24

    Google Scholar 

  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 2:2310–2317

    Article  Google Scholar 

  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 30:326–339

    Article  Google Scholar 

  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 39:3115–3141

    Article  Google Scholar 

  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 2:780–800

    Article  Google Scholar 

  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 107:56–60

    Article  Google Scholar 

  21. Norton MG, Sahaym U (2012) Lithium-ion batteries with nanostructured electrodes and associated methods of making. US Patent

  22. Liu XH, Zhong L, Mao SX, Zhu T, Huang JY (2012) Size-dependent fracture of silicon nanoparticles during lithiation. ACS Nano 6:1522–1531

    Article  Google Scholar 

  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 7:3427–3433

    Article  Google Scholar 

  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 223:50–55

    Article  Google Scholar 

  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 11:2251–2258

    Article  Google Scholar 

  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 8:915–922

    Article  Google Scholar 

  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 13:758–764

    Article  Google Scholar 

  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 6:8439–8447

    Article  Google Scholar 

  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 4:1–6

    Google Scholar 

  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 7:2914–2922

    Article  Google Scholar 

  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 11:3991–3997

    Article  Google Scholar 

  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 13:4876–4883

    Article  Google Scholar 

  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 332:192–197

    Article  Google Scholar 

  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 128:408–411

    Article  Google Scholar 

  35. Wang B, Luo B, Li X, Zhi L (2012) The dimensionality of Sn anodes in Li-ion batteries. Mater Today 15:544–552

    Article  Google Scholar 

  36. Sides CR, Li N, Patrissi CJ, Scrosati B, Martin CR (2002) Nanoscale materials for lithium-ion batteries. MRS Bull 27:604–607

    Article  Google Scholar 

  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 628:407–412

    Article  Google Scholar 

  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 278:660–667

    Article  Google Scholar 

  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 28:275–279

    Article  Google Scholar 

  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 131:15984–15985

    Article  Google Scholar 

  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 2:4192

    Article  Google Scholar 

  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 143:35–37

    Article  Google Scholar 

  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 2:1314–1321

    Article  Google Scholar 

  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 121:345–351

    Article  Google Scholar 

  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

    Article  Google Scholar 

  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. 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):1878–1879

    Google Scholar 

  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 4:156–157

    Google Scholar 

  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-3454-3451-3452

  50. Winter M, Besenhard JO (1999) Electrochemical lithiation of tin and tin-based intermetallics and composites. Electrochim Acta 45:31–50

    Article  Google Scholar 

  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–F3024

    Article  Google Scholar 

  52. Nesper R, Schnering H (1987) Li21Sn5, a Zintl phase as well as a Hume-Rothery phase. J Solid State Chem 70:48–57

    Article  Google Scholar 

  53. Lupu C, Mao J-G, Rabalais JW, Guloy AM, Richardson JW (2003) X-ray and neutron diffraction studies on “Li4.4Sn”. Inorg Chem 42:3765–3771

    Article  Google Scholar 

  54. Wagner RS, Ellis WC (1964) Vapor-liquid-solid mechanism of single crystal growth. Appl Phys Lett 4:89–90

    Article  Google Scholar 

  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 21:2681–2702

    Article  Google Scholar 

  56. McIlroy DN, Zhang D, Kranov Y, Norton MG (2001) Nanosprings. Appl Phys Lett 79:1540–1542

    Article  Google Scholar 

  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

    Article  Google Scholar 

  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 66:1–7

    Article  Google Scholar 

  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 3:31–35

    Article  Google Scholar 

  60. Kukovitsky EF, Lvov SG, Sainov NA (2000) VLS-growth of carbon nanotubes from the vapor. Chem Phys Lett 317:65–70

    Article  Google Scholar 

  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 17:367–374

    Article  Google Scholar 

  62. Djenizian T, Hanzu I, Eyraud M, Santinacci L (2008) Electrochemical fabrication of tin nanowires: A short review. C R Chimie 11:995–1003

    Article  Google Scholar 

  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 52:7820–7826

    Article  Google Scholar 

  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 25:265402

    Article  Google Scholar 

  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. 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 9:4379–4389

    Article  Google Scholar 

Download references

Acknowledgements

This work was performed at Sandia National Laboratories at the Center for Integrated Nanotechnologies, a DOE-BES supported national user facility. Sandia National Laboratories is a multiprogram laboratory managed and operated by Sandia Corporation, a Lockheed Martin Corporation, for the U.S. Department of Energy’s National Nuclear Security Administration under contract DEAC04-94AL85000.

Author information

Author notes

  1. Yang Liu

    Present address: Department of Materials Science & Engineering, North Carolina State University, Raleigh, NC, 27695, USA

Authors and Affiliations

  1. Department of Materials Science & Engineering, University of Connecticut, 97 North Eagleville Road, Unit 3136, Storrs, CT, 06269, USA

    Matthew T. Janish & C. Barry Carter

  2. School of Mechanical and Materials Engineering, Washington State University, Pullman, WA, 99164, USA

    David T. Mackay & M. Grant Norton

  3. Center for Integrated Nanotechnologies, Sandia National Laboratories, Albuquerque, NM, 87185, USA

    Yang Liu, Katherine L. Jungjohann & C. Barry Carter

  4. Department of Chemical & Biomolecular Engineering, University of Connecticut, 191 Auditorium Road, Storrs, CT, 06269, USA

    C. Barry Carter

  5. Institute of Materials Science, University of Connecticut, 97 North Eagleville Road, Storrs, CT, 06269-3136, USA

    C. Barry Carter

Authors
  1. Matthew T. Janish
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. David T. Mackay
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yang Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Katherine L. Jungjohann
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. C. Barry Carter
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. M. Grant Norton
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Matthew T. Janish.

Ethics declarations

Conflict of Interest

The authors declare that they have no conflict of interest.

Disclosures

MTJ is supported by a GAANN Fellowship from the Department of Education. YL and KLJ acknowledge support as part of the Nanostructures for Electrical Energy Storage (NEES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under award number DESC0001160.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Janish, M.T., Mackay, D.T., Liu, Y. et al. TEM in situ lithiation of tin nanoneedles for battery applications. J Mater Sci 51, 589–602 (2016). https://doi.org/10.1007/s10853-015-9318-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-015-9318-0

Keywords

Search

Navigation