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Enabling the high capacity of lithium-rich anti-fluorite lithium iron oxide by simultaneous anionic and cationic redox

Nature Energy volume 2, pages 963–971 (2017)Cite this article

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Abstract

Anionic redox reactions in cathodes of lithium-ion batteries are allowing opportunities to double or even triple the energy density. However, it is still challenging to develop a cathode, especially with Earth-abundant elements, that enables anionic redox activity for real-world applications, primarily due to limited strategies to intercept the oxygenates from further irreversible oxidation to O2 gas. Here we report simultaneous iron and oxygen redox activity in a Li-rich anti-fluorite Li5FeO4 electrode. During the removal of the first two Li ions, the oxidation potential of O2− is lowered to approximately 3.5 V versus Li+/Li0, at which potential the cationic oxidation occurs concurrently. These anionic and cationic redox reactions show high reversibility without any obvious O2 gas release. Moreover, this study provides an insightful guide to designing high-capacity cathodes with reversible oxygen redox activity by simply introducing oxygen ions that are exclusively coordinated by Li+.

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Fig. 1: Phase conversion of LFO during electrochemical cycling.
Fig. 2: Morphology and structure change of Li5FeO4 during the first charge.
Fig. 3: In situ electrochemical impedance spectra of Li5FeO4 during the first charge.
Fig. 4: Evolution of iron and oxygen in the first charge.
Fig. 5: Effect of Li6–O configurations on the electronic states of O ions in cation DRPs.
Fig. 6: Onset voltage for O2 gas release from Li5FeO4
Fig. 7: Reversibility of the Fe3+/Fe4+ redox couple.
Fig. 8: Schematic of the structural change and redox reactions in Li5FeO4 during electrochemical cycling.

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References

  1. Whittingham, M. S. Lithium batteries and cathode materials. Chem. Rev. 104, 4271–4301 (2004).

    Article  Google Scholar 

  2. Sathiya, M. et al. Reversible anionic redox chemistry in high-capacity layered-oxide electrodes. Nat. Mater. 12, 827–835 (2013).

    Article  Google Scholar 

  3. McCalla, E. et al. Visualization of O–O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries. Science 350, 1516–1521 (2015).

    Article  Google Scholar 

  4. McCalla, E. et al. Understanding the roles of anionic redox and oxygen release during electrochemical cycling of lithium-rich layered Li4FeSbO6. J. Am. Chem. Soc. 137, 4804–4814 (2015).

    Article  Google Scholar 

  5. Luo, K. et al. Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen. Nat. Chem. 8, 684–691 (2016).

    Article  Google Scholar 

  6. Seo, D.-H. et al. The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials. Nat. Chem. 8, 692–697 (2016).

    Article  Google Scholar 

  7. Sathiya, M. et al. Electron paramagnetic resonance imaging for real-time monitoring of Li-ion batteries. Nat. Commun. 6, 6276 (2015).

  8. Grimaud, A., Hong, W., Shao-Horn, Y. & Tarascon, J.-M. Anionic redox processes for electrochemical devices. Nat. Mater. 15, 121–126 (2016).

    Article  Google Scholar 

  9. Freire, M. et al. A new active Li–Mn–O compound for high energy density Li-ion batteries. Nat. Mater. 15, 173–177 (2016).

    Article  Google Scholar 

  10. Pearce, P. E. et al. Evidence for anionic redox activity in a tridimensional-ordered Li-rich positive electrode β-Li2IrO3. Nat. Mater. 16, 580–586 (2017).

    Article  Google Scholar 

  11. Zhu, Z. et al. Anion-redox nanolithia cathodes for Li-ion batteries. Nat. Energy 1, 16111 (2016).

    Article  Google Scholar 

  12. Okuoka, S.-i et al. A new sealed lithium-peroxide battery with a Co-doped Li2O cathode in a superconcentrated lithium bis(fluorosulfonyl)amide electrolyte. Sci. Rep. 4, 5684 (2014).

    Article  Google Scholar 

  13. Ogasawara, Y. et al. Charge/discharge mechanism of a new Co-doped Li2O cathode material for a rechargeable sealed lithium-peroxide battery analyzed by X-ray absorption spectroscopy. J. Power Sources 287, 220–225 (2015).

    Article  Google Scholar 

  14. Harada, K. et al. Electrochemical reactions and cathode properties of Fe-doped Li2O for the hermetically sealed lithium peroxide battery. J. Power Sources 322, 49–56 (2016).

    Article  Google Scholar 

  15. Narukawa, S. et al. Anti-fluorite type Li6CoO4, Li5FeO4, and Li6MnO4 as the cathode for lithium secondary batteries. Solid State Ionics 122, 59–64 (1999).

    Article  Google Scholar 

  16. Imanishi, N. et al. Antifluorite compounds, Li5+xFe1−xCoxO4, as a lithium intercalation host. J. Power Sources 146, 21–26 (2005).

    Article  Google Scholar 

  17. Noh, M. & Cho, J. Role of Li6CoO4 cathode additive in Li-ion cells containing low coulombic efficiency anode material. J. Electrochem. Soc. 159, A1329–A1334 (2012).

    Article  Google Scholar 

  18. Lim, Y.-G. et al. Anti-fluorite Li6CoO4 as an alternative lithium source for lithium ion capacitors: an experimental and first principles study. J. Mater. Chem. A 3, 12377–12385 (2015).

    Article  Google Scholar 

  19. Kirklin, S., Chan, M. K. Y., Trahey, L., Thackeray, M. M. & Wolverton, C. High-throughput screening of high-capacity electrodes for hybrid Li-ion-Li-O2 cells. Phys. Chem. Chem. Phys. 16, 22073–22082 (2014).

    Article  Google Scholar 

  20. Johnson, C. et al. Li2O removal from Li5FeO4: A cathode precursor for lithium-ion batteries. Chem. Mater. 22, 1263–1270 (2010).

    Article  Google Scholar 

  21. Trahey, L. et al. Activated lithium-metal-oxides as catalytic electrodes for Li–O2 cells. Electrochem. Solid-State Lett. 14, A64–A66 (2011).

    Article  Google Scholar 

  22. Thackeray, M. M., Chan, M. K. Y., Trahey, L., Kirklin, S. & Wolverton, C. Vision for designing high-energy, hybrid Li ion/Li–O2 cells. J. Phys. Chem. Lett. 4, 3607–3611 (2013).

    Article  Google Scholar 

  23. Hirano, A. et al. Electrochemical properties and Mössbauer effect of anti-fluorite type compound, Li5FeO4. Solid State Ionics 176, 2777–2782 (2005).

    Article  Google Scholar 

  24. Okumura, T., Shikano, M. & Kobayashi, H. Effect of bulk and surface structural changes in Li5FeO4 positive electrodes during first charging on subsequent lithium-ion battery performance. J. Mater. Chem. A 2, 11847–11856 (2014).

    Article  Google Scholar 

  25. Maroni, V. A., Johnson, C. S., Rood, S. C. M., Kropf, A. J. & Bass, D. A. Characterization of novel lithium battery cathode materials by spectroscopic methods: The Li5+xFeO4 system. Appl. Spectrosc. 67, 903–912 (2013).

    Article  Google Scholar 

  26. Gilmore, K. et al. Efficient implementation of core-excitation Bethe–Salpeter equation calculations. Comput. Phys. Commun. 197, 109–117 (2015).

    Article  MathSciNet  Google Scholar 

  27. Vinson, J., Rehr, J. J., Kas, J. J. & Shirley, E. L. Bethe-Salpeter equation calculations of core excitation spectra. Phys. Rev. B 83, 115106 (2011).

    Article  Google Scholar 

  28. Mizokawa, T. et al. Role of oxygen holes in LixCoO2 revealed by soft X-ray spectroscopy. Phys. Rev. Lett. 111, 056404 (2013).

    Article  Google Scholar 

  29. Su, X. et al. A new strategy to mitigate the initial capacity loss of lithium ion batteries. J. Power Sources 324, 150–157 (2016).

    Article  Google Scholar 

  30. McCloskey, B. D., Bethune, D., Shelby, R., Girishkumar, G. & Luntz, A. Solvents’ critical role in nonaqueous lithium–oxygen battery electrochemistry. J. Phys. Chem. Lett. 2, 1161–1166 (2011).

    Article  Google Scholar 

  31. Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Rad. 12, 537–541 (2005).

    Article  Google Scholar 

  32. Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).

    Article  Google Scholar 

  33. Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251–14269 (1994).

    Article  Google Scholar 

  34. Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).

    Article  Google Scholar 

  35. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    Article  Google Scholar 

  36. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

    Article  Google Scholar 

  37. Perdew, J. P., Ernzerhof, M. & Burke, K. Rationale for mixing exact exchange with density functional approximations. J. Chem. Phys. 105, 9982–9985 (1996).

    Article  Google Scholar 

  38. Wang, L., Maxisch, T. & Ceder, G. Oxidation energies of transition metal oxides within the GGA + U framework. Phys. Rev. B 73, 195107 (2006).

    Article  Google Scholar 

  39. Zhou, F., Marianetti, C. A., Cococcioni, M., Morgan, D. & Ceder, G. Phase separation in LixFePO4 induced by correlation effects. Phys. Rev. B 69, 201101 (2004).

    Article  Google Scholar 

  40. Kirklin, S. et al. The Open Quantum Materials Database (OQMD): assessing the accuracy of DFT formation energies. npj Comput. Mater 1, 15010–15024 (2015).

    Article  Google Scholar 

  41. Saal, J. E., Kirklin, S., Aykol, M., Meredig, B. & Wolverton, C. Materials design and discovery with high-throughput density functional theory: The Open Quantum Materials Database (OQMD). JOM 65, 1501–1509 (2013).

    Article  Google Scholar 

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Acknowledgements

This work was supported by the Centre for Electrochemical Energy Science, an Energy Frontier Research Centre funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under award number DE-AC02–06CH11. Use of the Advanced Photon Source and the Centre for Nanoscale Materials, both Office of Science user facilities operated for DOE, Office of Science by Argonne National Laboratory, was supported by the US DOE under Contract No. DE-AC02-06CH11357. The authors acknowledge C.-K. Lin and X. Wang for preparing the Li5FeO4 powders and electrodes. L.L. and M.K.Y.C. thank E. Shirley and J. Vinson for the use of and guidance with the OCEAN code. The computing resources are supported by the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the US Department of Energy under Contract DE-AC02-05CH11231, and Blues, a high-performance computing cluster operated by the Laboratory Computing Resource Center at Argonne National Laboratory.

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  1. Chun Zhan and Zhenpeng Yao contributed equally to this work.

Authors and Affiliations

  1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL, USA

    Chun Zhan, Jun Lu, Victor A. Maroni, Eungje Lee, Christopher Johnson, Michael M. Thackeray & Khalil Amine

  2. Material Science and Engineering Department, Northwestern University, Evanston, IL, USA

    Zhenpeng Yao & Chris Wolverton

  3. X-ray Science Division, Argonne National Laboratory, Argonne, IL, USA

    Lu Ma, Esen E. Alp, Tianpin Wu & Yang Ren

  4. Centre for Nanoscale Materials, Argonne National Laboratory, Argonne, IL, USA

    Liang Li, Jianguo Wen & Maria K. Y. Chan

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  1. Chun Zhan
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Contributions

C.Z. and J.L. conceived the idea and design of the experiments. Z.Y. and C.W. performed the DFT simulations. L.M. and T.W. carried out the measurements and analysis of XAS. V.A.M. performed the fitting of Raman spectra. J.W performed the TEM imaging. L.L. and M.K.Y.C. performed the oxygen core-level spectrum simulations. E.L. and E.E.A performed the measurements and analysis of ex situ Mössbauer spectroscopy. Y.R. contributed to measurements of in situ and ex situ XRD. C.J. and M.M.T. contributed to discussions and interpretation of the data. The project was supervised by J.L. and K.A.

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Correspondence to Jun Lu, Chris Wolverton or Khalil Amine.

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Supplementary Figure 1–8, Supplementary Table 1–2, Supplementary Notes, Supplementary References.

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Zhan, C., Yao, Z., Lu, J. et al. Enabling the high capacity of lithium-rich anti-fluorite lithium iron oxide by simultaneous anionic and cationic redox. Nat Energy 2, 963–971 (2017). https://doi.org/10.1038/s41560-017-0043-6

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