Abstract
Layered lithium nickel-rich oxides, Li[Ni1−xMx]O2 (M=metal), have attracted significant interest as the cathode material for rechargeable lithium batteries owing to their high capacity, excellent rate capability and low cost1,2,3,4,5,6,7. However, their low thermal-abuse tolerance and poor cycle life, especially at elevated temperature, prohibit their use in practical batteries4,5,6. Here, we report on a concentration-gradient cathode material for rechargeable lithium batteries based on a layered lithium nickel cobalt manganese oxide. In this material, each particle has a central bulk that is rich in Ni and a Mn-rich outer layer with decreasing Ni concentration and increasing Mn and Co concentrations as the surface is approached. The former provides high capacity, whereas the latter improves the thermal stability. A half cell using our concentration-gradient cathode material achieved a high capacity of 209 mA h g−1 and retained 96% of this capacity after 50 charge–discharge cycles under an aggressive test profile (55 ∘C between 3.0 and 4.4 V). Our concentration-gradient material also showed superior performance in thermal-abuse tests compared with the bulk composition Li[Ni0.8Co0.1Mn0.1]O2 used as reference. These results suggest that our cathode material could enable production of batteries that meet the demanding performance and safety requirements of plug-in hybrid electric vehicles.
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References
Kostecki, R. & McLarnon, F. Local-probe studies of degradation of composite LiNi0.8Co0.15Al0.05O2 cathodes in high-power lithium-ion cells. Electrochem. Solid State Lett. 7, A380–A383 (2004).
Dahn, J. R., Fuller, E. W., Obrovac, M. & Sacken, U. von. Thermal stability of LixCoO2, LixNiO2 and λ-MnO2 and consequences for the safety of Li-ion cells. Solid State Ionics 69, 265–270 (1994).
Arai, H. et al. Electrochemical and thermal behavior of LiNi1−zMzO2 (M=Co, Mn, Ti). J. Electrochem. Soc. 144, 3117–3125 (1997).
Shim, J. et al. Electrochemical analysis for cycle performance and capacity fading of a lithium-ion battery cycled at elevated temperature. J. Power Sources 112, 222–230 (2002).
Wright, R. B. et al. Power fade and capacity fade resulting from cycle-life testing of advanced technology development program lithium-ion batteries. J. Power Sources 112, 865–869 (2003).
Belharouak, I., Lu, W., Vissers, D. & Amine, K. Safety characteristics of Li(Ni0.8Co0.15Al0.05)O2 and Li(Ni1/3Co1/3Mn1/3)O2 . Electrochem. Commun. 8, 329–335 (2006).
Kim, M.-H., Shin, H.-S., Shin, D. & Sun, Y.-K. Synthesis and electrochemical properties of Li[Ni0.8Co0.1Mn0.1]O2 and Li[Ni0.8Co0.2]O2 via co-precipitation. J. Power Sources 159, 1328–1333 (2006).
FreedomCAR PHEV battery test manual, <http://www.uscar.org>.
Sun, Y.-K. et al. Synthesis and characterization of Li[(Ni0.8Co0.1Mn0.1)0.8–(Ni0.5Mn0.5)0.2]O2 with the microscale core–shell structure as the positive electrode material for lithium batteries. J. Am. Chem. Soc. 127, 13411–13418 (2005).
Ohzuku, T. & Makimura, Y. Layered lithium insertion material of LiNi1/2Mn1/2O2: A possible alternative to LiCoO2 for advanced lithium-ion batteries. Chem. Lett. 30, 744–745 (2001).
Lu, Z., MacNeil, D. D. & Dahn, J. R. Layered cathode materials Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 for lithium-ion batteries. Electrochem. Solid-State Lett. 4, A191–A194 (2001).
Kim, J.-S., Johnson, C. S. & Thackeray, M. M. Layered xLiMO2·(1−x)Li2M′O3 electrodes for lithium batteries: A study of 0.95LiMn0.5Ni0.5O2·0.05Li2TiO3 . Electrochem. Commun. 4, 205–209 (2002).
Sun, Y.-K., Myung, S.-T., Park, B.-C. & Amine, K. Synthesis of spherical nano- to microscale core–shell particles Li[(Ni0.8Co0.1Mn0.1)1−x(Ni0.5Mn0.5)x]O2 and their applications to lithium batteries. Chem. Mater. 18, 5199–5163 (2006).
Sun, Y. K. et al. Novel core–shell-structured Li[(Ni0.8Co0.2)0.8(Ni0.5Mn0.5)0.2]O2 via coprecipitation as positive electrode material for lithium secondary batteries. J. Phys. Chem. B 110, 6810–6815 (2006).
Koyama, Y. et al. Crystal and electronic structures of superstructural Li1−x[Co1/3Ni1/3Mn1/3]O2 (0≤x≤1). J. Power Sources 119-121, 644–648 (2003).
Myung, S.-T. et al. Synthesis of Li[(Ni0.5Mn0.5)1−xLix]O2 by emulsion drying method and impact of excess Li on structural and electrochemical properties. Chem. Mater. 18, 1658–1666 (2006).
Lee, K.-S. et al. Structural and electrochemical properties of layered Li[Ni1−2xCoxMnx]O2 (x=0.1–0.3) positive electrode materials for Li-ion batteries. J. Electrochem. Soc. 154, A971–A977 (2007).
Cho, J. et al. Storage characteristics of LiNi0.8Co0.1+xMn0.1−xO2 (x=0, 0.03, and 0.06) cathode materials for lithium batteries. J. Electrochem. Soc 155, A239–A245 (2008).
Abraham, D. P. et al. Microscopy and spectroscopy of lithium nickel oxide-based particles used in high power lithium-ion cells. J. Electrochem. Soc. 150, A1450–A1456 (2003).
Striebel, K. A. et al. Diagnostic analysis of electrodes from high-power lithium-ion cells cycled under different conditions. J. Electrochem. Soc. 151, A857–A866 (2004).
Woo, S.-U. Improvement of electrochemical performances of Li[Ni0.8Co0.1Mn0.1]O2 cathode materials by fluorine substitution. J. Electrochem. Soc. 154, A649–A655 (2007).
Lee, M.-H., Kang, Y.-J., Myung, S.-T. & Sun, Y.-K. Synthetic optimization of Li[Ni1/3Co1/3Mn1/3]O2 via co-precipitation. Electrochim. Acta 50, 939–948 (2004).
Dahn, J. R. et al. A comparison of the electrode/electrolyte reaction at elevated temperatures for various Li-ion battery cathodes. J. Power Sources 108, 8–14 (2002).
Acknowledgements
This work was supported by the Global Research Network Program in collaboration with the US Department of Energy’s Argonne National Laboratory.
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Sun, YK., Myung, ST., Park, BC. et al. High-energy cathode material for long-life and safe lithium batteries. Nature Mater 8, 320–324 (2009). https://doi.org/10.1038/nmat2418
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DOI: https://doi.org/10.1038/nmat2418
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