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On electrochemistry of Al2O3-coated LiCoO2 composite cathode with improved cycle stability

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Abstract

LiCoO2-based cathode does still have a powerful competition in high-end mobile electronics due to its relatively high true density (about 5.2 g/cm3). When the operation potential range is extended, the improvement in its cycle stability has attracted more attention. The extension of its operation potential can be realized by partial replacement of Co by Ni and Mn or by surface modification. However, Ni and Mn replacing partial Co results in decreased true density; for example, the true density of LiNi0.5Mn0.3Co0.2O2 is about 4.6 g/cm3. In this case, the increase in its practical energy density is impossible. As a result, the surface modification technology becomes very important to extend its operation potential range. In this article, an Al2O3-coated LiCoO2 cathode was synthesized. X-ray diffraction test did not show any impurity. Scanning electron spectroscopy measurements showed that the basic microstructure of pristine LiCoO2 grain is sustained after coating Al2O3. The surface characteristic of pure and Al2O3-coated LiCoO2 was also analyzed using an X-ray photoelectron spectroscopy (XPS) technique. Unusual XPS peaks of O 1s, Al 2p, and Co 2p binding energy were found and may be caused by the possible H existence in crystal structure. The electrochemical behavior was systematically investigated, and the cathode was cycled at different charge cutoff voltages (4.30∼4.60 V). The charge-discharge and cyclic voltammetry measurements showed an obviously improved cyclic performance after coating Al2O3. The electrocatalytic activity is not clearly changed before and after coating Al2O3. From our systematical investigation, it could be concluded that the Al2O3-coated LiCoO2 cathode is suitable for practical application in the potential range of 3.70∼4.50 V vs. Li/Li+.

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References

  1. Teo LP, Buraidah MH, Arof AK (2015) A novel LiSnVO4 anode material for lithium-ion batteries. Ionics 21(8):2393–2399

    Article  CAS  Google Scholar 

  2. Mueller F, Bresser D, Chakravadhanula VSK, Passerini S (2015) Fe-doped SnO2 nanoparticles as new high capacity anode material for secondary lithium-ion batteries. J Power Sources 299:398–402

    Article  CAS  Google Scholar 

  3. Tian BB, Światowska J, Maurice V, Zanna S, Seyeux A, Marcus P (2015) Binary iron-chromium oxide as negative electrode for lithium-ion micro-batteries—spectroscopic and microscopic characterization. Appl Surf Sci 353:1170–1178

    Article  CAS  Google Scholar 

  4. Koetschau I, Richard MN, Dahn JR (1995) Orthorhombic LiMnO2 as a high capacity cathode for Li-ion cells. J Electrochem Soc 142(9):2906–2910

    Article  CAS  Google Scholar 

  5. Wang R, Li X, Liu L, Lee J, Seo DH, Bo SH, Urban A, Ceder G (2015) A disordered rock-salt Li-excess cathode material with high capacity and substantial oxygen redox activity: Li1.25Nb0.25Mn0.5O2. Electrochem Commun 60:70–73

    Article  CAS  Google Scholar 

  6. Hwang I, Lee CW, Kim JC, Yoon SH (2012) Particle size effect of Ni-rich cathode materials on lithium ion battery performance. Mater Res Bull 47:73–78

    Article  CAS  Google Scholar 

  7. Lee EH, Park JH, Kim JM, Lee SY (2013) Direct surface modification of high-voltage LiCoO2 cathodes by UV-cured nanothickness poly(ethylene glycol diacrylate) gel polymer electrolytes. Electrochim Acta 104:249–254

    Article  CAS  Google Scholar 

  8. Myung ST, Kumagai N, Komaba S, Chung HT (2001) Effects of Al doping on the microstructure of LiCoO2 cathode materials. Solid State Ionics 139:47–56

    Article  CAS  Google Scholar 

  9. Mukhopadhyay A, Sheldon BW (2014) Deformation and stress in electrode materials for Li-ion batteries. Prog Mater Sci 63:58–116

    Article  CAS  Google Scholar 

  10. Xu X, Lee S, Jeong S, Kim Y, Cho J (2013) Recent progress on nanostructured 4V cathode materials for Li-ion batteries for mobile electronics. Mater Today 16(12):487–495

    Article  CAS  Google Scholar 

  11. Oh S, Lee JK, Byun D, Cho WI, Cho BW (2004) Effect of Al2O3 coating on electrochemical performance of LiCoO2 as cathode materials for secondary lithium batteries. J Power Sources 132:249–255

    Article  CAS  Google Scholar 

  12. Moon SM, Chang W, Byun D, Lee JK (2010) Comparative studies on ZnO-coated and uncoated LiCoO2 cycled at various rates and temperatures. Curr Appl Phys 10:122–126

    Article  Google Scholar 

  13. Takeuchi T, Kyun T, Morimoto H, Tobishima S (2011) Influence of surface modification of LiCoO2 by organic compounds on electrochemical and thermal properties of Li/LiCoO2 rechargeable cells. J Power Sources 196:2790–2801

    Article  CAS  Google Scholar 

  14. Hao Q, Xu C, Jia S, Zhao X (2013) Improving the cycling stability of LiCoO2 at 4.5 V through surface modification by Fe2O3 coating. Electrochim Acta 113:439–445

    Article  CAS  Google Scholar 

  15. Antolini E, Giorgi L, Carewska M (1999) Formation of Li- and Mg-doped LiCoO2 powders: a BET analysis. J Mater Sci Lett 18:325–327

    Article  CAS  Google Scholar 

  16. Kim KC, Jegal JP, Bak SM, Roh KC, Kim KB (2014) Improved high-voltage performance of FePO4-coated LiCoO2 by microwave-assisted hydrothermal method. Electrochem Commun 43:113–116

    Article  CAS  Google Scholar 

  17. Kim Y, Veith GM, Nanda J, Unocic RR, Chi M, Dudney NJ (2011) High voltage stability of LiCoO2 particles with a nano-scale Lipon coating. Electrochim Acta 56(19):6573–6580

    Article  CAS  Google Scholar 

  18. Dahheron L, Dedryvere R, Martinez H, Flahaut D, Menetrier M, Delmas C, Gonbeau D (2009) Possible explanation for the efficiency of Al-based coatings on LiCoO2: surface properties of LiCo1-xAlxO2 solid solution. Chem Mater 21:5607–5616

    Article  Google Scholar 

  19. Sun YK, Cho SW, Myung ST, Amine K, Prakash J (2007) Effect of AlF3 coating amount on high voltage cycling performance of LiCoO2. Electrochim Acta 53:1013–1019

    Article  CAS  Google Scholar 

  20. Kosova NV, Devyatkina ET (2007) Comparative study of LiCoO2 surface modified with different oxides. J Power Sources 174:959–964

    Article  CAS  Google Scholar 

  21. Bueno PR, Pesquero NC, Ferreira FF, Santiago EI, Varela JA, Longo E (2008) Voltage-composition profile and synchrotron X-ray structural analysis of low and high temperature LixCoO2 host material. J Phys Chem C 112:14655–14664

    Article  CAS  Google Scholar 

  22. Okumura T, Yamaguchi Y, Shikano M, Kobayashi H (2012) Correlation of lithium ion distribution and X-ray absorption near-edge structure in O3- and O2-lithium cobalt oxides from first-principle calculation. J Mater Chem 22:17340–17348

    Article  CAS  Google Scholar 

  23. Li L, Li X, Wang Z, Guo H, Yue P, Chen W, Wu L (2011) A simple and effective method to synthesize layered LiNi0.8Co0.1Mn0.1O2 cathode materials for lithium ion battery. Powder Technol 206:353–357

    Article  CAS  Google Scholar 

  24. Tan KS, Reddy MV, Rao GVS, Chowdari BVR (2005) High-performance LiCoO2 by molten salt (LiNO3:LiCl) synthesis for Li-ion batteries. J Power Sources 147:241–248

    Article  CAS  Google Scholar 

  25. Huang J, Yang J, Li W, Cai W, Jiang Z (2008) Electrochemical properties of LiCoO2 thin film electrode prepared by ink-jet printing technique. Thin Solid Films 516:3314–3319

    Article  CAS  Google Scholar 

  26. Xu Y, Chen C, Wang X, Lei Y, Wang Q (2002) The cycle life and surface properties of Ti-based AB2 metal hydride electrodes. J Alloys Compd 337:214–220

    Article  CAS  Google Scholar 

  27. Zhang T, He Y, Wang F, Li H, Duan C, Wu C (2014) Surface analysis of cobalt-enriched crushed products of spent lithium-ion batteries by X-ray photoelectron spectroscopy. Sep Purif Technol 138:21–27

    Article  CAS  Google Scholar 

  28. Appapillai AT, Mansour AN, Cho J, Horn YS (2007) Microstructure of LiCoO2 with and without AlPO4 nanoparticle coating: combined STEM and XPS studies. Chem Mater 19:5748–5757

    Article  CAS  Google Scholar 

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Acknowledgments

The financial support by the National Natural Science Foundation of China (Nos. 51272167 and 51572181) is greatly appreciated.

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Correspondence to Ruizhi Yang or Yanhui Xu.

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Chen, G., Geng, H., Wang, Z. et al. On electrochemistry of Al2O3-coated LiCoO2 composite cathode with improved cycle stability. Ionics 22, 629–636 (2016). https://doi.org/10.1007/s11581-015-1590-0

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  • DOI: https://doi.org/10.1007/s11581-015-1590-0

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