Abstract
The search for new materials that could improve the energy density of Li-ion batteries is one of today’s most challenging issues. Many families of transition metal oxides as well as transition metal polyanionic frameworks have been proposed during the past twenty years1,2. Among them, manganese oxides, such as the LiMn2O4 spinel or the overlithiated oxide Li[Li1/3Mn2/3]O2, have been intensively studied owing to the low toxicity of manganese-based materials and the high redox potential of the Mn3+/Mn4+ couple. In this work, we report on a new electrochemically active compound with the ‘Li4Mn2O5’ composition, prepared by direct mechanochemical synthesis at room temperature. This rock-salt-type nanostructured material shows a discharge capacity of 355 mAh g−1, which is the highest yet reported among the known lithium manganese oxide electrode materials. According to the magnetic measurements, this exceptional capacity results from the electrochemical activity of the Mn3+/Mn4+ and O2−/O− redox couples, and, importantly, of the Mn4+/Mn5+ couple also.
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References
Ellis, B. L. et al. Positive electrode materials for Li-ion and Li-batteries. Chem. Mater. 22, 691–714 (2010).
Song, H. K. et al. Recent progress in nanostructured cathode materials for lithium secondary batteries. Adv. Funct. Mater. 20, 3818–3834 (2010).
Tarascon, J. M. Key challenges in future Li-battery research. Phil. Trans. R. Soc. A 368, 3227–3241 (2010).
Amatucci, G. et al. Optimization of insertion compounds such as LiMn2O4 for Li-ion batteries. J. Electrochem. Soc. 149, K31–K46 (2002).
Thackeray, M. M. et al. Structural fatigue in spinel electrodes in high voltage (4V) Li/LixMn2O4 cells. Electrochem. Solid State Lett. 1, 7–9 (1998).
Jang, D. H. et al. Electrolyte effects on spinel dissolution and cathodic capacity losses in 4 V Li/LiMn2O4 cells. J. Electrochem. Soc. 143, 2204–2211 (1996).
Huang, H. et al. Correlating capacity loss of stoichiometric and nonstoichiometric lithium manganese oxide spinel electrodes with their structural integrity. J. Electrochem. Soc. 146, 3649–3654 (1999).
Shin, Y. et al. Factors influencing the capacity fade of spinel lithium manganese oxides. J. Electrochem. Soc. 151, A204–A208 (2004).
Deng, B. H. et al. Capacity fading with oxygen loss for manganese spinels upon cycling at elevated temperatures. J. Power Sources 180, 864–868 (2008).
Xia, Y. G. et al. Improved cycling performance of oxygen-stoichiometric spinel Li1+xAlyMn2−x−yO4+δ at elevated temperature. Electrochim. Acta 52, 4708–4714 (2007).
Kim, J. S. et al. 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).
Kim, J. S. et al. Electrochemical and structural properties of xLi2M′O3 ⋅ (1 − x)LiMn0.5Ni0.5O2 electrodes for lithium batteries (M′ = Ti, Mn, Zr; 0 ≤ x ≤ 0.3). Chem. Mater. 16, 1996–2006 (2004).
Martha, S. K. et al. Surface studies of high voltage lithium rich composition: Li1.2Mn0.525Ni0.175Co0.1O2 . J. Power Sources 216, 179–186 (2012).
Tran, N. et al. Mechanisms associated with the ‘plateau’ observed at high voltage for the overlithiated Li1.12(Ni0.425Mn0.425Co0.15)0.88O2 system. Chem. Mater. 20, 4815–4825 (2008).
Koga, H. et al. Reversible oxygen participation to the redox processes revealed for Li1.20Mn0.54Co0.13Ni0.13O2 . J. Electrochem. Soc. 160, A786–A792 (2013).
Sathiya, M. et al. Reversible anionic redox chemistry in high-capacity layered-oxide electrodes. Nature Mater. 12, 827–835 (2013).
Armstrong, A. R. et al. Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2 . J. Am. Chem. Soc. 128, 8694–8698 (2006).
Kosova, N. V. et al. Electronic state of cobalt and oxygen ions in stoichiometric and nonstoichiometric Li1+xCoO2 before and after delithiation according to XPS and DRS. J. Power Sources 119–121, 669–673 (2003).
Whittingam, M. S. Inorganic nanomaterials for batteries. Dalton Trans. 40, 5424–5431 (2008).
Kim, D. K. et al. Spinel LiMn2O4 nanorods as lithium ion battery cathodes. Nano Lett. 8, 3948–3952 (2008).
Kosova, N. V. et al. Synthesis of nanosized materials for lithium-ion batteries by mechanical activation. Studies of their structure and properties. Russ. J. Electrochem. 48, 351–361 (2012).
Jiao, F. et al. Synthesis of ordered mesoporous Li–Mn–O spinel as a positive electrode for rechargeable lithium batteries. Angew. Chem. Int. Ed. 47, 9711–9716 (2008).
Popa, N. C. The (hkl) dependence of diffraction-line broadening caused by strain and size for all laue groups in Rietveld refinement. J. Appl. Crystallogr. 31, 176–180 (1998).
Kittel, C. Introduction to Solid State Physics 8th Edition 308 (John Wiley, 2005).
Greedan, J. E. et al. Long range and short range magnetic order in orthorhombic LiMnO2 . J. Solid State Chem. 128, 209–214 (1997).
Lu, J. et al. Magnetism in lithium–oxygen discharge product. ChemSusChem 6, 1196–1202 (2013).
Gummow, R. J. et al. Improved capacity retention in rechargeable 4V lithium/lithium–manganese oxide (spinel) cells. Solid State Ion. 69, 59–67 (1994).
Kim, D. et al. Comments on stabilizing layered manganese oxide electrodes for Li batteries. Electrochem. Commun. 36, 103–106 (2013).
Davidson, I. J. et al. Lithium-ion cell based on orthorhombic LiMnO2 . J. Power Sources 54, 232–235 (1995).
Johnson, C. S. Development and utility of manganese oxides as cathodes in lithium batteries. J. Power Sources 165, 559–565 (2007).
Acknowledgements
The authors gratefully acknowledge S. Gascoin for her help in numerous XRPD collections. The authors gratefully acknowledge the CNRS.
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M.F., N.V.K. and V.P. contributed to the synthesis of the materials and performed the electrochemical and chemical analysis. M.F. and A.M. performed the magnetic analysis of the samples. D.C. analysed the XRPD data and O.I.L. carried out the TEM analysis. C.J., N.V.K. and V.P. conceived and designed the project. All the authors contributed to writing the paper.
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Freire, M., Kosova, N., Jordy, C. et al. A new active Li–Mn–O compound for high energy density Li-ion batteries. Nature Mater 15, 173–177 (2016). https://doi.org/10.1038/nmat4479
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DOI: https://doi.org/10.1038/nmat4479
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