Real-time in situ TEM studying the fading mechanism of tin dioxide nanowire electrodes in lithium ion batteries

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Fading mechanism of tin dioxide (SnO2) electrodes in lithium ion batteries has attracted much attentions, which is of great importance for the battery applications. In this paper, electrochemical lithiation-delithiation cycles of individual SnO2 nanowires were conducted in situ in a high-resolution transmission electron microscopy (TEM). Major changes in volume with expansions of 170%∼300% on SnO2 nanowire electrodes were observed during the first lithiation process in electrochemical cycling, including conversion reaction of SnO2 precursor to Li2O matrix and active lithium host Sn, and alloying of Sn with Li to form brittle Li-Sn alloy. SnO2 nanowire electrodes were inclined to suffer from thermal runaway condition in the first two cycles. During cycling, morphology and composition evolution of SnO2 nanowire electrodes were recorded. Cyclic lithiation and delithiation of the electrode demonstrated the phase transition between Li13Sn5 and Sn. Metallic Sn clusters were formed and their sizes enlarged with increasing cycle times. Detrimental aggregation of Sn clusters caused pulverization in SnO2 nanowire electrodes, which broke the conduction and transport path for electrons and lithium ions. The real-time in situ TEM revealed fading mechanism provides important guidelines for the viable design of the SnO2 nanowire electrodes in lithium ion batteries.

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  1. 1

    Tarascon J M, Armand M. Issues and challenges facing rechargeable lithium batteries. Nature, 2001, 414: 359–367

  2. 2

    Chan C K, Peng H L, Liu G, et al. High performance lithium bat tery anodes using silicon nanowires. Nat Nanotechnol, 2008, 3: 31–35

  3. 3

    Zhao K J, Pharr M, Vlassak J J, et al. Fracture of elcetrodes in lithiumion batteries caused by fast charging. J Appl Phys, 2010, 108: 073517

  4. 4

    Wang H F, Jang Y, Huang B Y, et al. TEM study of electrochemical cycling-induced damage and disorder in LiCoO2 cathodes for rechargeable lithium batteries. J Electrochem Soc, 1999, 146: 473–480

  5. 5

    Bhattacharya S, Riahi A R, Alpas A T. In-situ observations of lithiation/de-lithiation induced graphite damage during electrochemical cycling. Scripta Mater, 2011, 64: 165–168

  6. 6

    Arara P, White R E, Doyle M. Capacity fade mechanisms and side reactions in lithium ion batteries. J Electroche Soc, 1998, 145: 3647–3667

  7. 7

    Idota Y, Mishima M, Miyaki Y, et al. European Pat, 1995, 651: 450A1

  8. 8

    Idota Y, Kubota T, Matsufuji A, et al. Tin-based amorphous oxide: A high-capacity lithium-ion-storage material. Science, 1997, 276: 1395–1397

  9. 9

    Brousse T, Retouxf R, Herterich U, et al. Thin-film crystalline SnO2-lithium electrodes. J Electrochem Soc, 1998, 145: 1–4

  10. 10

    Wang Y, Zeng H C, Lee J Y. Highly reversible lithium storage in porous SnO2 nanotubes with coaxially grown carbon nanotube overlayers. Adv Mater, 2006, 18: 645–649

  11. 11

    Courtney I A, Dahn J R. Electrochemical and in situ X-ray diffraction studies of the reaction of lithium with tin oxide composites. J Electrochem Soc, 1997, 144: 2045–2052

  12. 12

    Courtney I A, Dahn J R. Key factors controlling the reversibility of the reaction of lithium with SnO2 and Sn2BPO6 glass. J Electrochem Soc, 1997, 144: 2943–2948

  13. 13

    Courtney I A, McKinnon W R, Dahna J R. On the aggregation of tin in SnO composite glasses caused by the reversible reaction with lithium. J Electrochem Soc, 1999, 146: 59–68

  14. 14

    Winter M, Besenhard J O, Albering J H, et al. Lithium storage alloys as anode materials for lithium ion batteries. Progress in Batteries and Battery Materials, 1998, 17: 208–213

  15. 15

    Wang C M, Xu W, Liu J, et al. In situ transmission electron microscopy observation of microstructure and phase evolution in a SnO2 nanowire during lithium intercalation. Nano Lett, 2011, 11: 1874–1880

  16. 16

    Zhang L Q, Xiao X H, Perng Y C, et al. Direct observation of Sn crystal growth during the lithiation and delithiation processes of SnO2 nanowires. Micron, 2012, 43: 1127–1133

  17. 17

    Gao P, Kang Z C, Fu W Y, et al. Electrically driven redox process in cerium oxides. J Am Chem Soc, 2010, 132: 4197–4201

  18. 18

    Wang L F, Tian X Z, Yang S Z, et al. Dynamic nanomechanics of zinc oxide nanowires. Appl Phys Lett, 2012, 100: 163110

  19. 19

    Yang S Z, Wang L F, Tian X Z, et al. Piezotronic effect of zinc oxide nanowires studied by in situ TEM. Adv Mater, 2012, 24: 4676–4682

  20. 20

    Liu Y, Hudak N S, Huber D L, et al. In situ transmission electron microscopy observation of pulverization of aluminum nanowires and evolution of the thin surface Al2O3 layers during lithiation delithiation cycles. Nano Lett, 2011, 11: 4188–4194

  21. 21

    Brousse T, Defives D, Pasquereau L, et al. Metal oxide anodes for Li-ion batteries. Ionics, 1997, 3: 332–337

  22. 22

    Hong J S, Maleki H, Hallaj S A, et al. Electrochemical-calorimetric studies of lithium-ion cells. J Electrochem Soc, 1998, 145: 1489–1501

  23. 23

    Jarzebski Z M, Marton J P. Physical properties of SnO2 materials: III. Optical properties. J Electrochem Soc, 1976, 123: 333C–346C

  24. 24

    Winter M, Besenhard J R O. Electrochemical lithiation of tin and tin-based intermetallics and composites. Electrochem Acta, 1999, 45: 31–50

  25. 25

    Woodford W H, Chiang Y M, Carterz W C. “Electrochemical shock” of intercalation electrodes: A fracture mechanics analysis. J Electrochem Soc, 2010, 157: A1052–A1059

  26. 26

    Viswanathan V V, Choi D, Wang D, et al. Effect of entropy change of lithium intercalation in cathodes and anodes on Li-ion battery thermal management. J Power Sources, 2010, 195: 3720–3729

  27. 27

    Li H, Huang X J, Chen L Q. Electrochemical impedance spectroscopy study of SnO2 and nano-SnO2 anodes in lithium rechargeable batteries. J Power Sources, 1999, 81: 340–345

  28. 28

    Kim C, Noh M, Choi M, et al. Critical size of a nano SnO2 electorde for Li-secondary battery. Chem Mater, 2005, 17: 3297–3301

  29. 29

    Aricò A S, Bruce P, Scrosati B, et al. Nanostructured materials for advanced energy conversion and storage devices. Nat Mater, 2005, 4: 366–377

  30. 30

    Poizot P, Laruelle S, Grugeon S, et al. Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries. Nature, 2000, 407: 496–499

  31. 31

    Huang J Y, Zhong L, Wang C M, et al. In situ observation of the electrochemical lithiation of a single SnO2 nanowire electrode. Science, 2010, 330: 1515–1520

  32. 32

    Liu X H, Huang J Y. In situ TEM electrochemistry of anode materials in lithium ion batteries. Energy Environ Sci, 2011, 4: 3844–3860

  33. 33

    Liu X H, Wang J W, Huang S, et al. In situ atomic-scale imaging of electrochemical lithiation in silicon. Nat Nanotechnol, 2012, 7: 749–756

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Correspondence to XueDong Bai.

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Wang, L., Xu, Z., Yang, S. et al. Real-time in situ TEM studying the fading mechanism of tin dioxide nanowire electrodes in lithium ion batteries. Sci. China Technol. Sci. 56, 2630–2635 (2013).

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  • lithium ion battery
  • tin dioxide nanowire electrode
  • fading mechanism
  • tin aggregation
  • in situ TEM