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Investigating surface morphology and cracking during lithiation of Al anodes

Department of Civil, Architectural and Environmental Engineering, University of Miami, Coral Gables, FL 33146, United States

This paper examines morphology and crack formation in Al anodes during lithiation. The morphological evolution during the lithiation of Al foils was studied using optical and scanning electron microscopy (SEM). X-ray diffraction (XRD) was utilized to evaluate the structural changes, and the uniaxial tensile test was employed to study the mechanical properties of lithiated Al. It was observed that the lithiation of Al consisted of nucleation and growth of LiAl nodules on the surface and their columnar growth in the thickness direction. Cracks were observed to initiate near the nodule peak and at the boundary between nodules. The effect of charge rate on the crystallite size and surface nodule size of LiAl is discussed. It was found that the stiffness and fracture strength of LiAl were lower than those of pristine Al.
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Keywords lithiation; Al anodes; cracks; nodules; SEM microscopy

Citation: Omid Gooranorimi, Ali Ghahremaninezhad. Investigating surface morphology and cracking during lithiation of Al anodes. AIMS Materials Science, 2016, 3(4): 1632-1648. doi: 10.3934/matersci.2016.4.1632


  • 1. Hatchard TD, Dahn JR (2004) In Situ XRD and Electrochemical Study of the Reaction of Lithium with Amorphous Silicon. J Electrochem Soc 151: A838–A842.    
  • 2. Larcher D, Beattie S, Morcrette M, et al. (2007) Recent findings and prospects in the field of pure metals as negative electrodes for Li-ion batteries. J Mater Chem 17: 3759–3772.    
  • 3. Nitta N, Yushin G (2013) High-Capacity Anode Materials for Lithium-Ion Batteries: Choice of Elements and Structures for Active Particles. Part Part Syst Charact 31: 317–336.
  • 4. Beaulieu LY, Cumyn VK, Eberman KW, et al. (2001) A system for performing simultaneous in situ atomic force microscopy/optical microscopy measurements on electrode materials for lithium-ion batteries. Rev Sci Instrum 72: 3313–3319.    
  • 5. McDowell MT, Lee SW, Nix WD, et al. (2013) 25th Anniversary Article: Understanding the Lithiation of Silicon and Other Alloying Anodes for Lithium-Ion Batteries. Adv Mater 25: 4966–4985.    
  • 6. Beaulieu LY, Eberman KW, Turner RL, et al. (2001) Colossal Reversible Volume Changes in Lithium Alloys. Electrochem Solid-State Lett 4: A137–A140.    
  • 7. Winter BM, Besenhard JO, Spahr ME, et al. (1998) Insertion Electrode Materials for Rechargeable Lithium Batteries. Adv Mater 10: 725–763.
  • 8. Kasavajjula U, Wang C, Appleby AJ (2007) Nano- and bulk-silicon-based insertion anodes for lithium-ion secondary cells. J Power Sources 163: 1003–1039.
  • 9. Liu XH, Zheng H, Zhong L, et al. (2011) Anisotropic swelling and fracture of silicon nanowires during lithiation. Nano Lett 11: 3312–3318.    
  • 10. Nishikawa K, Munakata H, Kanamura K (2013) In-situ observation of one silicon particle during the first charging. J Power Sources 243: 630–634.    
  • 11. Kalnaus S, Rhodes K, Daniel C (2011) A study of lithium ion intercalation induced fracture of silicon particles used as anode material in Li-ion battery. J Power Sources 196: 8116–8124.    
  • 12. Rhodes K, Dudney N, Lara-Curzio E, et al. (2010) Understanding the Degradation of Silicon Electrodes for Lithium-Ion Batteries Using Acoustic Emission. J Electrochem Soc 157: A1354–A1360.    
  • 13. Zhao K, Pharr M, Cai S, et al. (2011) Large Plastic Deformation in High-Capacity Lithium-Ion Batteries Caused by Charge and Discharge. J Am Ceram Soc 94: s226–s235.    
  • 14. Sethuraman VA, Nguyen A, Chon MJ, et al. (2013) Stress Evolution in Composite Silicon Electrodes during Lithiation/Delithiation. J Electrochem Soc 160: A739–A746.    
  • 15. Bower AF, Guduru PR, Sethuraman VA (2011) A finite strain model of stress, diffusion, plastic flow, and electrochemical reactions in a lithium-ion half-cell. J Mech Phys Solids 59: 804–828.    
  • 16. Melendres CA, Sy CC (1978) Structure and Cyclic Discharge Behavior of LiAl Electrodes. J Electrochem Soc 125: 727–731.    
  • 17. Wen CJ, Boukamp BA, Huggins RA (1979) Thermodynamic and Mass Transport Properties of “LiAl”. J Electrochem Soc 126: 2258–2266.    
  • 18. Besenhard JO, Hess M, Komenda P (1990) Dimensionally Stable Li-Alloy Electrodes for Secondary Batteries. Solid State Ionics 41: 525–529.
  • 19. Garreau M, Thevenin J, Fekir M, et al. (1983) On the processes responsible for the degradation of the aluminum-lithium electrode used as anode materials in lithium aprotic electrolyte batteries. J Power Sources 9: 235–238.
  • 20. Zaghib K, Gauthier M, Armand M (2003) Expanded metal a novel anode for Li-ion polymer batteries. J Power Sources 119–121: 76–83.
  • 21. Lei X, Wang C, Yi Z, Liang Y, et al. (2007) Effects of particle size on the electrochemical properties of aluminum powders as anode materials for lithium ion batteries. J Alloys Compd 429: 311–315.    
  • 22. Hamon Y, Brousse T, Jousse F, et al. (2001) Aluminum negative electrode in lithium ion batteries. J Power Sources 97–98: 185–187.
  • 23. Au M, McWhorter S, Ajo H, et al. (2010) Free standing aluminum nanostructures as anodes for Li-ion rechargeable batteries. J Power Sources 195: 3333–3337.    
  • 24. Kuksenko SP (2013) Aluminum foil as anode material of lithium-ion batteries: Effect of electrolyte compositions on cycling parameters. Russ J Electrochem 49: 67–75.    
  • 25. Sharma SK, Kim MS, Kim DY, et al. (2013) Al nanorod thin films as anode electrode for Li ion rechargeable batteries. Electrochim Acta 87: 872–879.    
  • 26. El Abedin SZ, Garsuch A, Endres F (2012) Aluminium Nanowire Electrodes for Lithium-Ion Batteries. Aust J Chem 65: 1529–1533.
  • 27. Leite MS, Ruzmetov D, Li Z, et al. (2014) Insights into capacity loss mechanisms of all-solid-state Li-ion batteries with Al anodes. J Mater Chem A 2: 20552–20559.    
  • 28. Beaulieu LY, Hatchard TD, Bonakdarpour A, et al. (2003) Reaction of Li with Alloy Thin Films Studied by In Situ AFM. J Electrochem Soc 150: A1457–A1464.    
  • 29. Owen JR, Maskell WC, Steele BCH, et al. (1984) Thin film lithium aluminium negative plate material. Solid State Ionics 13: 329–334.    
  • 30. Liu Y, Hudak NS, Huber DL, et al. (2011) 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 11: 4188–4194.    
  • 31. Hudak NS, Huber DL (2012) Size Effects in the Electrochemical Alloying and Cycling of Electrodeposited Aluminum with Lithium. J Electrochem Soc 159: A688–A695.    
  • 32. John C, Huggins RA (1980) Electrochemical Investigation of Solubility and Chemical Diffusion of Lithium in Aluminum. Metall Mater Trans B 11: 131–137.    
  • 33. Pollak E, Lucas IT, Kostecki R (2010) A study of lithium transport in aluminum membranes. Electrochem Commun 12: 198–201.    
  • 34. McDowell MT, Lee SW, Ryu I, et al. (2011) Novel size and surface oxide effects in silicon nanowires as lithium battery anodes. Nano Lett 11: 4018–4025.    
  • 35. Mittemeijer EJ, Welzel U (2008) The “state of the art” of the diffraction analysis of crystallite size and lattice strain. Zeitschrift Fur Krist 223: 552–560.
  • 36. Transactions ECS, Society TE (2011) Nanostructured lithium-aluminum alloy electrodes for lithium-ion batteries. ECS Trans 33: 1–13.
  • 37. Gao H (1990) Stress concentration at slightly undulating. J Mech Phys Solids 39: 443–458.
  • 38. Ruan S, Schuh CA (2008) Mesoscale structure and segregation in electrodeposited nanocrystalline alloys. Scr Mater 59: 1218–1221.    
  • 39. Bastos A, Zaefferer S, Raabe D, et al. (2006) Characterization of the microstructure and texture of nanostructured electrodeposited NiCo using electron backscatter diffraction (EBSD). Acta Mater 54: 2451–2462.
  • 40. Zhao K, Pharr M, Vlassak JJ, et al. (2010) Fracture of electrodes in lithium-ion batteries caused by fast charging. J Appl Phys 108: 073517.    
  • 41. Grantab R, Shenoy VB (2012) Pressure-Gradient Dependent Diffusion and Crack Propagation in Lithiated Silicon Nanowires. J Electrochem Soc 159: A584–A591.    
  • 42. Rice BJR (1969) On the ductile enlargement of voids in triaxial stress fields. J Phys Mech Solids 17: 201–217.
  • 43. Ghahremaninezhad A, Ravi-Chandar K (2012) Ductile failure behavior of polycrystalline Al 6061-T6. Int J Fract 174: 177–202.
  • 44. Kushima A, Huang JY, Li J (2012) Quantitative Fracture Strength and Plasticity Measurements of Lithiated Silicon Nanowires by In Situ TEM Tensile Experiments. ACS Nano 6: 9425–9432.    
  • 45. Zhao K, Pharr M, Wan Q, et al. (2012) Concurrent Reaction and Plasticity during Initial Lithiation of Crystalline Silicon in Lithium-Ion Batteries. J Electrochem Soc 159: A238–A243.    
  • 46. Zhao K, Wang WL, Gregoire J, et al. (2011) Lithium-assisted plastic deformation of silicon electrodes in lithium-ion batteries: a first-principles theoretical study. Nano Lett 11: 2962–2967.    
  • 47. Nadimpalli SPV, Sethuraman VA, Bucci G, et al. (2013) On Plastic Deformation and Fracture in Si Films during Electrochemical Lithiation/Delithiation Cycling. J Electrochem Soc 160: A1885–A1893.    


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Copyright Info: 2016, Ali Ghahremaninezhad, et al., licensee AIMS Press. This is an open access article distributed under the terms of the Creative Commons Attribution Licese (http://creativecommons.org/licenses/by/4.0)

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