Experimental Mechanics

, Volume 59, Issue 5, pp 681–689 | Cite as

In Situ Measurement of Phase Boundary Kinetics during Initial Lithiation of Crystalline Silicon through Picosecond Ultrasonics

  • S. Rezazadeh-Kalehbasti
  • L. W. Liu
  • H. J. Maris
  • P. R. GuduruEmail author


Studying the kinetics of phase transformation and phase boundary propagation during initial lithiation of silicon electrodes in lithium ion batteries is relevant to understanding their performance. Such studies are usually challenging due to the difficulties in measuring the phase boundary velocity in the interior of the sample. Here we introduce a non-invasive, in situ method to measure the progression of the phase boundary in a planar specimen geometry while maintaining well-controlled lithium flux and potential. We developed an apparatus integrating an electrochemical cell with picosecond ultrasonics to probe the propagating phase boundary in real time. Phase propagation during initial lithiation of crystalline silicon, which is an example of a high capacity anode, is investigated. The primary objective of this manuscript is to report on the experimental technique development and some preliminary results. For lithiation normal to the (100) plane, we observe the phase boundary velocity to be approximately 12 pm/s and x to be 3.73 in LixSi under galvanostatic lithiation with a current density of 40 μA/cm2. The growth rate of the lithiated phase and the reaction rate coefficient are examined using a Deal-Grove type model.


Picosecond ultrasonics In situ Phase boundary propagation Crystalline silicon Lithium ion battery 



This work was supported by the United States Department of Energy EPSCoR Implementation award (grant # DE-SC0007074).


  1. 1.
    Lin HN, Stoner RJ, Maris HJ, Tauc J (1991) Phonon attenuation and velocity measurements in transparent materials by picosecond acoustic interferometry. J Appl Phys 69:3816–3822CrossRefGoogle Scholar
  2. 2.
    Maris H (1998) Picosecond ultrasonics. Sci Am 64–67Google Scholar
  3. 3.
    Miao Q, Liu L-W, Grimsley TJ, Nurmikko AV, Maris HJ (2015) Picosecond ultrasonic measurements using an optical mask. Ultrasonics 56:141–147CrossRefGoogle Scholar
  4. 4.
    Rossignol C, Chigarev N, Ducousso M, Audoin B, Forget G, Guillemot F, Durrieu M-C (2008) In vitro picosecond ultrasonics in a single cell. App Phys Lett 93:123901CrossRefGoogle Scholar
  5. 5.
    Ducousso M, Zouani OE, Chanseau C, Chollet C, Rossignol C, Audoin B, Durrieu M-C (2013) Evaluation of mechanical properties of fixed bone cells with sub-micrometer thickness by picosecond ultrasonics. Eur Phys J Appl Phys 61(1):11201CrossRefGoogle Scholar
  6. 6.
    Casset F, Devos A, Sadtler S, Le Louarn A, Emery P, Le Rhun G, Ancey P, Fanget S, Defaÿ E (2012) Young modulus and poisson ratio of PZT thin film by picosecond ultrasonics. 2012 IEEE Int Ultrason Symp Proc 2180–2183Google Scholar
  7. 7.
    Mante PA, Robillard JF, Devos A (2008) Complete thin film mechanical characterization using picosecond ultrasonics and nanostructured transducers: experimental demonstration on SiO2. Appl Phys Lett 93:071909CrossRefGoogle Scholar
  8. 8.
    Msall ME, Wright OB, Matsuda O (2007) Seeking shear waves in liquids with picosecond ultrasonics. J Phys Conf Ser 92:012026CrossRefGoogle Scholar
  9. 9.
    Li J, Dahn JR (2007) An in situ x-ray diffraction study of the reaction of li with crystalline Si. J Electrochem Soc 154(3):A156–A161CrossRefGoogle Scholar
  10. 10.
    Kasavajjula U, Wang C, Appleby AJ (2007) Nano- and bulk-silicon-based insertion anodes for lithium-ion secondary cells. J Power Sources 163:1003–1039CrossRefGoogle Scholar
  11. 11.
    Fan F, Huang S, Yang H, Raju M, Datta D, Shenoy VB, van Duin ACT, Zhang S, Zhu T (2013) Mechanical properties of amorphous LixSi alloys: a reactive force field study. Model Simul Mater Sci Eng 21:074002CrossRefGoogle Scholar
  12. 12.
    Zhao K, Pharr M, Wan Q, Wang WL, Kaxiras E, Vlassak JJ, Suo Z (2012) Concurrent reaction and plasticity during initial lithiation of crystalline silicon in lithium-ion batteries. J Electrochem Soc 159(3):A238–A243CrossRefGoogle Scholar
  13. 13.
    Pharr M, Zhao K, Wang X, Suo Z, Vlassak JJ (2012) Kinetics of initial lithiation of crystalline silicon electrodes of lithium-ion batteries. Nano Lett 12:5039–5047CrossRefGoogle Scholar
  14. 14.
    Lee SW, McDowell MT, Choi JW, Cui Y (2011) Anomalous shape changes of silicon nanopillars by electrochemical lithiation. Nano Lett 11:3034–3039CrossRefGoogle Scholar
  15. 15.
    Lee SW, Berla LA, McDowell MT, Nix WD, Cui Y (2012) Reaction front evolution during electrochemical lithiation of crystalline silicon nanopillars. Isr J Chem 52:1118–1123CrossRefGoogle Scholar
  16. 16.
    An Y, Wood BC, Ye J, Chiang Y-M, Wang YM, Tang M, Jiang H (2015) Mitigating mechanical failure of crystalline silicon electrodes for lithium batteries by morphological design. Phys Chem Chem Phys 17:17718–17728CrossRefGoogle Scholar
  17. 17.
    Chon MJ, Sethuraman VA, McCormick A, Srinivasan V, Guduru PR (2011) Real-time measurement of stress and damage evolution during initial lithiation of crystalline silicon. Phys Rev Let 107:045503CrossRefGoogle Scholar
  18. 18.
    Sethuraman VA, Chon MJ, Shimshak M, Van Winkle N, Guduru PR (2010) In situ measurement of biaxial modulus of Si anode for li-ion batteries. Electrochem Commun 12:1614–1617CrossRefGoogle Scholar
  19. 19.
    Liu XH, Wang JW, Huang S, Fan F, Huang X, Liu Y, Krylyuk S, Yoo J, Dayeh SA, Davydov AV, Mao SX, Picraux ST, Zhang S, Li J, Zhu T, Huang JY (2012) In situ atomic-scale imaging of electrochemical lithiation in silicon. Nat Nanotechnol 7:749–756CrossRefGoogle Scholar
  20. 20.
    Fister TT, Goldman JL, Long BR, Nuzzo RG, Gewirth AA, Fenter PA (2013) X-ray diffraction microscopy of lithiated silicon microstructures. Appl Phys Lett 102:131903CrossRefGoogle Scholar
  21. 21.
    Cao C, Steinrück H-G, Shyam B, Stone KH, Toney MF (2016) In situ study of silicon electrode lLithiation with x-ray reflectivity. Nano Lett 16:7394–7401CrossRefGoogle Scholar
  22. 22.
    Seidlhofer B-K, Jerliu B, Trapp M, Hüger E, Risse S, Cubitt R, Schmidt H, Steitz R, Ballauff M (2016) Lithiation of crystalline silicon as analyzed by operando neutron reflectivity. ACS Nano 10:7458–7466CrossRefGoogle Scholar
  23. 23.
    Yang H, Fan F, Liang W, Guo X, Zhu T, Zhang S (2014) A chemo-mechanical model of lithiation in silicon. J Mech Phys Solids 70:349–361CrossRefGoogle Scholar
  24. 24.
    Thomsen C, Grahn HT, Maris HJ, Tauc J (1986) Surface generation and detection of phonons by picosecond light pulses. Phys Rev B 34(6):4129–4138CrossRefGoogle Scholar
  25. 25.
    Yoon I, Abraham DP, Lucht BL, Bower AF, Guduru PR (2016) In situ measurement of solid electrolyte interphase evolution on silicon anodes using atomic force microscopy. Adv Energy Mater 6(12):1600099CrossRefGoogle Scholar
  26. 26.
    Epoxy Technology, Inc (2017) EPO-TEK302-3M Technical Data SheetGoogle Scholar
  27. 27.
    Nadimpalli SPV, Sethuraman VA, Dalavi S, Lucht B, Chon MJ, Shenoy VB, Guduru PR (2012) Quantifying capacity loss due to solid-electrolyte-interphase layer formation on silicon negative electrodes in lithium-ion batteries. J Power Sources 215:145–151CrossRefGoogle Scholar
  28. 28.
    Beaulieu LY, Hatchard TD, Bonakdarpour A, Fleischauer MD, Dahn JR (2003) Reaction of li with alloy thin films studied by in situ AFM. J Electrochem Soc 150(11):A1457–A1464CrossRefGoogle Scholar
  29. 29.
    Shenoy VB, Johari P, Qi Y (2010) Elastic softening of amorphous and crystalline li–Si phases with increasing li concentration: a first-principles study. J Power Sources 195:6825–6830CrossRefGoogle Scholar
  30. 30.
    Kim H, Chou C-Y, Ekerdt JG, Hwang GS (2011) Structure and properties of li-Si alloys: a first-principles study. J Phys Chem C 115:2514–2252CrossRefGoogle Scholar
  31. 31.
    Deal BE, Grove AS (1965) General relationship for the thermal oxidation of silicon. J Appl Phys 3770–3778Google Scholar
  32. 32.
    Chen C-H, Chason E, Guduru PR (2017) Measurements of the phase and stress evolution during initial lithiation of Sn electrodes. J Electrochem Soc 164(4):A574–A579CrossRefGoogle Scholar

Copyright information

© Society for Experimental Mechanics 2019

Authors and Affiliations

  1. 1.School of EngineeringBrown UniversityProvidenceUSA
  2. 2.Department of PhysicsBrown UniversityProvidenceUSA

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