Skip to main content

Advertisement

SpringerLink
Log in

Real-Time Stress Measurement in SiO2 Thin Films during Electrochemical Lithiation/Delithiation Cycling

  • Published:
Experimental Mechanics Aims and scope Submit manuscript

Abstract

Oxide coatings have been shown to improve the cyclic performance of high-energy density electrode materials such as Si. However, no study exists on the mechanical characterization of these oxide coatings. Here, thin film SiO2 electrodes are cycled under galvanostatic conditions (at C/9 rate) in a half-cell configuration with lithium metal foil as counter/reference electrode, with 1 M LiPF6 in ethylene carbonate, diethyl carbonate, dimethyl carbonate solution (1:1:1, wt%) as electrolyte. Stress evolution in the SiO2 thin film electrodes during electrochemical lithiation/delithiation is measured in situ by monitoring the substrate curvature using a multi-beam optical sensing method. Upon lithiation SiO2 undergoes extensive inelastic deformation, with a peak compressive stress of 3.1 GPa, and upon delithiation the stress became tensile with a peak stress of 0.7 GPa. A simple plane strain finite element model of Si nanotube coated with SiO2 shell was developed to understand the mechanical response of the core-shell type microstructures under electrochemical cycling; measured stress response was used in the model to represent SiO2 constitutive behavior while Si was treated as an elastic-plastic material with concentration dependent mechanical properties obtained from the literature. The results reported here provide insights and quantitative understanding as to why the highly brittle SiO2 coatings are able to sustain significant volume expansion (300%) of Si core without fracture and enhance cyclic performance of Si reported in the literature. Also, the basic mechanical properties presented here are necessary first step for future design and development of durable Si/SiO2 core shell structures or SiO2-based electrodes.

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. Kasavajjula U, Wang C, Appleby AJ (2007) Nano- and bulk-silicon-based insertion anodes for lithium-ion secondary cells. J Power Sources 163:1003

    Article  Google Scholar 

  2. Besenhard JO, Yang J, Winter M (1997) Will advanced lithium-alloy anodes have a chance in lithium-ion batteries? J Power Sources 68:87

    Article  Google Scholar 

  3. Beaulieu LY, Eberman KW, Turner RL, Krause LJ, Dahn JR (2001) Colossal reversible volume changes in lithium alloys. Electrochem Solid State Lett 4:A137

    Article  Google Scholar 

  4. Beaulieu LY, Hatchard TD, Bonakdarpour A, Fleischaue MD, Dahn JR (2003) Reaction of li with alloy thin films studied by in situ AFM. J Electrochem Soc 150:A1457

    Article  Google Scholar 

  5. Aurbach D (2000) Review of selected electrode–solution interactions which determine the performance of li and li ion batteries. J Power Sources 89:206

    Article  Google Scholar 

  6. Aurbach D, Moshkovich M, Cohen Y, Schechter A (1999) Study of surface film formation on noble-metal electrodes in alkyl carbonates/li salt solutions, using simultaneous in situ AFM, EQCM, FTIR, and EIS. Langmuir 15:2947

    Article  Google Scholar 

  7. Peled E (1979) Electrochemical behavior of alkali and alkaline earth metals in nonaqueous battery systems - the solid electrolyte interphase model. J Electrochem Soc 126(12):2047

    Article  Google Scholar 

  8. Besenhard JO, Winter M, Yang J, Biberacher W (1995) Filming mechanism of lithium-carbon anodes in organic and inorganic electrolytes. J Power Sources 54:228

    Article  Google Scholar 

  9. Nadimpalli SPV, Sethuraman VA, Dhalavi 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

    Article  Google Scholar 

  10. Kostecki R, McLarnon F (2003) Microprobe study of the effect of li intercalation on the structure of graphite. J Power Sources 119-121:550

    Article  Google Scholar 

  11. Vetter J, Novák P, Wagner MR, Veit C, Möller K-C, Besenhard JO, Winter M, Wohlfahrt-Mehrens M, Vogler C, Hammoushe A (2005) Ageing mechanisms in lithium-ion batteries. J Power Sources 147:269

    Article  Google Scholar 

  12. Lee YM, Lee JY, Shim H, Lee JK, Park J (2007) SEI layer formation on amorphous Si thin electrode during precycling. J Electrochem Soc 154:A515

    Article  Google Scholar 

  13. McDowell MT, Lee SW, Ryu I, Wu H, Nix WD, Choi JW, Cui Y (2011) Novel size and surface oxide effects in silicon nanowires as lithium battery anodes. Nano Lett 11(9):4018

    Article  Google Scholar 

  14. 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

    Article  Google Scholar 

  15. Wu H, Cui Y (2012) Designing nanostructured Si anodes for high energy lithium ion batteries. Nano Today 7:414

    Article  Google Scholar 

  16. Wu H, Yu G, Pan L, Liu N, McDowell MT, Bao Z, Cui Y (2013) Stable li-ion battery anodes by in-situ polymerization of conducting hydrogel to conformally coat silicon nanoparticles. Nat Commun 4:1943

    Google Scholar 

  17. Zhang Y, Li Y, Wang Z, Zhao K (2014) Lithiation of SiO2 in li-ion batteries: in situ transmission electron microscopy experiments and theoretical studies. Nano Lett 14:7161

    Article  Google Scholar 

  18. Choi S, Jung DS, Choi JW (2014) Scalable fracture-free SiOC glass coating for robust silicon nanoparticle anodes in lithium secondary batteries. Nano Lett 14:7120

    Article  Google Scholar 

  19. Sun Q, Zhang B, Fu Z-W (2008) Lithium electrochemisty of SiO2 thin film electrode for lithium-ion batteries. Appl Surf Sci 254:3774–3779

    Article  Google Scholar 

  20. Chang W-S, Park C-M, Kim J-H, Kim Y-U, Jeong G, Sohn H-J (2012) Quartz (SiO2): a new energy storage anode material for li-ion batteries. Energy Environ Sci 5:6895–6899

    Article  Google Scholar 

  21. Miyachi M, Yamamoto H, Kawai H, Ohta T, Shirakata M (2005) Analysis of SiO anodes for lithium-ion batteries. J Electrochem Soc 152(10):A2089–A2091

    Article  Google Scholar 

  22. Favors Z, Wang W, Bay HH, George A, Ozkan M, Ozkan CS (2014) Stable cycling of SiO2 nanotubes as high-performance anodes for Lithium-ion batteries. Sci Rep 4:4605

    Article  Google Scholar 

  23. Guo B, Shu J, Wang Z, Yang H, Shi L, Liu Y, Chen L (2008) Electrochemical reduction of Nano-SiO2 in hard carbon as anode material for Lithium ion batteries. Electrochem Commun 10:1876–1878

    Article  Google Scholar 

  24. Yan N, Wang F, Zhong H, Liu Y, Wang Y, Hu L, Chen Q (2013) Hollow porous SiO2 Nanocubes towards high-performance anodes for Lithium-ion batteries. Sci Rep 3:1568

    Article  Google Scholar 

  25. Philippe B, Dedryvere R, Gorgoi M, Rensmo H, Gonbeau D, Edstrom K (2013) Improved performance of Nanosilicon electrodes using the salt LiFSI: a photoelectron spectroscopy study. J Am Chem Soc 135:9829–9842

    Article  Google Scholar 

  26. Nadimpalli SPV, Tripuraneni R, Sethuraman VA (2015) Real-time stress measurements in germanium thin film electrodes during electrochemical Lithiation/Delithiation cycling. J Electrochem Soc 162(4):A2840–A2846

    Article  Google Scholar 

  27. Sethuraman VA, Chon MJ, Shimshak M, Srinivasan V, Guduru PR (2010) In situ measurements of stress evolution in silicon thin films during electrochemical Lithiation and Delithiation. J Power Sources 195(15):5062

    Article  Google Scholar 

  28. Zhao K, Wang WL, Gregoire J, Pharr M, Suo Z, Vlassak JJ, Kaxiras E (2011) Lithium-assisted plastic deformation of silicon electrodes in lithium-ion batteries: a first-principles theoretical study. Nano Lett 11(7):2962

    Article  Google Scholar 

  29. Al-Obeidi A, Kramer D, Thompson CV, Monig R (2015) Mechanical stresses and morphology evolution in germanium thin film electrodes during Lithiation and Delithiation. J Power Sources 297:472–480

    Article  Google Scholar 

  30. Boles ST, Sedlmayr A, Kraft O, Monig R (2012) In situ cycling and mechanical testing of silicon nanowire anodes for Lithium-ion battery applications. Appl Phys Lett 100:243901

    Article  Google Scholar 

  31. Sheth J, Karan NK, Abraham DP, Nguyen CC, Lucht BL, Sheldon BW, Guduru PR (2016) In situ stress evolution in Li1+xMn2O4 thin films during electrochemical cycling in li-ion cells. J Electrochem Soc 163(13):A2524–A2530

    Article  Google Scholar 

  32. Freund LB, Suresh S (2004) Thin films materials: stress, defect formation and surface evolution. Cambridge University Press, Cambridge

    Book  MATH  Google Scholar 

  33. Ryu I, Choi JW, Cui Y, Nix WD (2011) Size-dependent fracture of Si nanowire battery anodes. J Mech Phys Solids 59:1717

    Article  Google Scholar 

  34. Abaqus (2016) Abaqus Reference Manuals, Dassault Systèmes Simulia Corp., Providence

  35. Zhang X, Shyy W, Sastry AM (2007) Numerical simulation of intercalation-induced stress in li-ion battery electrode particles. J Electrochem Soc 154(10):A910–A916

    Article  Google Scholar 

  36. Sethuraman VA, Srinivasan V, Bower AF, Guduru PR (2010) In situ measurements of stress-potential coupling in lithiated silicon. J Electrochem Soc 157(11):A1253–A1261

    Article  Google Scholar 

  37. Ostadhossein A, Kim S-Y, Cubuk ED, Qi Y, van Duin AC (2016) Atomic insight into the lithium storage and diffusion mechanism of SiO2/Al2O3 electrodes of lithium ion batteries: ReaxFF reactive force field modeling. J Phys Chem A 120(13):2114–2127

    Article  Google Scholar 

  38. Bucci G, Nadimpalli SP, Sethuraman VA, Bower AF, Guduru PR (2014) Measurement and modeling of the mechanical and electrochemical response of amorphous Si thin film electrodes during cyclic lithiation. J Mech Phys Solids 62:276–294

    Article  Google Scholar 

  39. Santimetaneedol A, Tripuraneni R, Chester SA, Nadimpalli SP (2016) Time-dependent deformation behavior of polyvinylidene fluoride binder: implications on the mechanics of composite electrodes. J Power Sources 332:118–128

    Article  Google Scholar 

  40. Wang H, Nadimpalli SP, Shenoy VB (2016) Inelastic shape changes of silicon particles and stress evolution at binder/particle interface in a composite electrode during lithiation/delithiation cycling. Extreme Mech Lett 9:430–438

    Article  Google Scholar 

  41. Tu J, Yuan Y, Zhan P, Jiao H, Wang X, Zhu H, Jiao S (2014) Straightforward approach toward SiO2 Nanospheres and their superior lithium storage performance. J Phys Chem C 118:7357–7362

    Article  Google Scholar 

  42. WN Sharpe Jr, J Pulskamp, DS Gianola, C Eberl, RG Polcawich, RJ Thompson (2006) Strain measurements of silicon dioxide microspecimens by digital imaging processing. Exp Mech. 47;(5):649–658

  43. Hutchinson JW, Suo Z (1991) Mixed mode cracking in layered materials. Adv Appl Mech 29:63–191

Download references

Acknowledgements

Authors would gratefully acknowledge funding from the National Science Foundation through the grant no NSF-CMMI-1652409 and from the New Jersey Institute of Technology through faculty seed grant 2016.

Author information

Authors and Affiliations

  1. Department of Mechanical Engineering, New Jersey Institute of Technology, Newark, NJ, 07102, USA

    S. P. V. Nadimpalli

Authors
  1. S. Rakshit
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. R. Tripuraneni
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. S. P. V. Nadimpalli
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to S. P. V. Nadimpalli.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Rakshit, S., Tripuraneni, R. & Nadimpalli, S.P.V. Real-Time Stress Measurement in SiO2 Thin Films during Electrochemical Lithiation/Delithiation Cycling. Exp Mech 58, 537–547 (2018). https://doi.org/10.1007/s11340-017-0371-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11340-017-0371-2

Keywords

Search

Navigation