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Non-topotactic reactions enable high rate capability in Li-rich cathode materials

Nature Energy volume 6, pages 706–714 (2021)Cite this article

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Abstract

High-rate cathode materials for Li-ion batteries require fast Li transport kinetics, which typically rely on topotactic Li intercalation/de-intercalation because it minimally disrupts Li transport pathways. In contrast to this conventional view, here we demonstrate that the rate capability in a Li-rich cation-disordered rocksalt cathode can be significantly improved when the topotactic reaction is replaced by a non-topotactic reaction. The fast non-topotactic lithiation reaction is enabled by facile and reversible transition metal octahedral-to-tetrahedral migration, which improves rather than impedes Li transport. Using this concept, we show that high-rate performance can be achieved in Mn- and Ni-based cation-disordered rocksalt materials when some of the transition metal content can reversibly switch between octahedral and tetrahedral sites. This study provides a new perspective on the design of high-performance cathode materials by demonstrating how the interplay between Li and transition metal migration in materials can be conducive to fast non-topotactic Li intercalation/de-intercalations.

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Fig. 1: Structural characterization of Li1.2Mn0.4−xTi0.4CrxO2.
Fig. 2: Electrochemistry of Li1.2Mn0.4−xTi0.4CrxO2 at room temperature.
Fig. 3: Redox mechanism and structural change of Li1.2Mn0.4−xTi0.4CrxO2.
Fig. 4: Effect of TM migration on Li kinetics.
Fig. 5: Structural characterization and electrochemistry of Li1.2Ni0.2−xTi0.6−xCr2xO2.

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All data generated and analysed during this study are included in the published article and its Supplementary Information. Source data are provided with this paper.

References

  1. Kang, K., Meng, Y. S., Bréger, J., Grey, C. P. & Ceder, G. Electrodes with high power and high capacity for rechargeable lithium batteries. Science 311, 977–980 (2006).

    Article  Google Scholar 

  2. Schougaard, S. B., Bréger, J., Jiang, M., Grey, C. P. & Goodenough, J. B. LiNi0.5+δMn0.5–δO2—A high-rate, high-capacity cathode for lithium rechargeable batteries. Adv. Mater. 18, 905–909 (2006).

    Article  Google Scholar 

  3. Julien, C. & Nazri, G. A. in Handbook of Advanced Electronic and Photonic Materials and Devices (ed. Singh Nalwa, H.) Ch. 3 (Academic Press, 2001).

  4. Jacobson, A. J. & Nazar, L. F. Intercalation Chemistry. Encyclopedia of Inorganic and Bioinorganic Chemistry https://doi.org/10.1002/9781119951438.eibc0093 (2011).

  5. Wu, F. & Yushin, G. Conversion cathodes for rechargeable lithium and lithium-ion batteries. Energy Environ. Sci. 10, 435–459 (2017).

    Article  Google Scholar 

  6. Wiaderek, K. M. et al. Comprehensive insights into the structural and chemical changes in mixed-anion FeOF electrodes by using operando PDF and NMR spectroscopy. J. Am. Chem. Soc. 135, 4070–4078 (2013).

    Article  Google Scholar 

  7. Yu, H.-C. et al. Designing the next generation high capacity battery electrodes. Energy Environ. Sci. 7, 1760–1768 (2014).

    Article  Google Scholar 

  8. Huang, Q. et al. Fading mechanisms and voltage hysteresis in FeF2–NiF2 solid solution cathodes for lithium and lithium-ion batteries. Small 15, 1804670 (2019).

    Article  Google Scholar 

  9. Hua, X. et al. Comprehensive study of the CuF2 conversion reaction mechanism in a lithium ion battery. J. Phys. Chem. C 118, 15169–15184 (2014).

    Article  Google Scholar 

  10. Bréger, J. et al. Effect of high voltage on the structure and electrochemistry of LiNi0.5Mn0.5O2: a joint experimental and theoretical study. Chem. Mater. 18, 4768–4781 (2006).

    Article  Google Scholar 

  11. Li, H. H. et al. Changes in the cation ordering of layered O3 LixNi0.5Mn0.5O2 during electrochemical cycling to high voltages: an electron diffraction study. Chem. Mater. 19, 2551–2565 (2007).

    Article  Google Scholar 

  12. Jones, C. D. W., Rossen, E. & Dahn, J. R. Structure and electrochemistry of LixCryCo1−yO2. Solid State Ion. 68, 65–69 (1994).

    Article  Google Scholar 

  13. Lyu, Y. et al. Atomic insight into electrochemical inactivity of lithium chromate (LiCrO2): irreversible migration of chromium into lithium layers in surface regions. J. Power Sources 273, 1218–1225 (2015).

    Article  Google Scholar 

  14. Lee, J. et al. Unlocking the potential of cation-disordered oxides for rechargeable lithium batteries. Science 343, 519–522 (2014).

    Article  Google Scholar 

  15. Clément, R. J., Lun, Z. & Ceder, G. Cation-disordered rocksalt transition metal oxides and oxyfluorides for high energy lithium-ion cathodes. Energy Environ. Sci. 13, 345–373 (2020).

    Article  Google Scholar 

  16. Balasubramanian, M., McBreen, J., Davidson, I. J., Whitfield, P. S. & Kargina, I. In situ X-ray absorption study of a layered manganese-chromium oxide-based cathode material. J. Electrochem. Soc. 149, A176–A184 (2002).

    Article  Google Scholar 

  17. Yang, W. & Devereaux, T. P. Anionic and cationic redox and interfaces in batteries: advances from soft X-ray absorption spectroscopy to resonant inelastic scattering. J. Power Sources 389, 188–197 (2018).

    Article  Google Scholar 

  18. Dai, K. et al. High reversibility of lattice oxygen redox quantified by direct bulk probes of both anionic and cationic redox reactions. Joule 3, 518–541 (2019).

    Article  Google Scholar 

  19. Li, N. et al. Correlating the phase evolution and anionic redox in Co-free Ni-rich layered oxide cathodes. Nano Energy 78, 105365 (2020).

    Article  Google Scholar 

  20. Papp, J. K. et al. A comparison of high voltage outgassing of LiCoO2, LiNiO2, and Li2MnO3 layered Li-ion cathode materials. Electrochim. Acta 368, 137505 (2021).

    Article  Google Scholar 

  21. Renfrew, S. E. & McCloskey, B. D. Residual lithium carbonate predominantly accounts for first cycle CO2 and CO outgassing of Li-stoichiometric and Li-rich layered transition-metal oxides. J. Am. Chem. Soc. 139, 17853–17860 (2017).

    Article  Google Scholar 

  22. Renfrew, S. E. & McCloskey, B. D. Quantification of surface oxygen depletion and solid carbonate evolution on the first cycle of LiNi0.6Mn0.2Co0.2O2 electrodes. ACS Appl. Energy Mater. 2, 3762–3772 (2019).

    Article  Google Scholar 

  23. Van der Ven, A. & Ceder, G. Lithium diffusion mechanisms in layered intercalation compounds. J. Power Sources 97–98, 529–531 (2001).

    Google Scholar 

  24. Van der Ven, A. Lithium diffusion in layered LixCoO. Electrochem. Solid-State Lett. 3, 301 (1999).

    Article  Google Scholar 

  25. Urban, A., Lee, J. & Ceder, G. The configurational space of rocksalt-type oxides for high-capacity lithium battery electrodes. Adv. Energy Mater. 4, 1400478 (2014).

    Article  Google Scholar 

  26. Reed, J. & Ceder, G. Role of electronic structure in the susceptibility of metastable transition-metal oxide structures to transformation. Chem. Rev. 104, 4513–4534 (2004).

    Article  Google Scholar 

  27. Shannon, R. D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr. A 32, 751–767 (1976).

    Article  Google Scholar 

  28. Ji, H. et al. Hidden structural and chemical order controls lithium transport in cation-disordered oxides for rechargeable batteries. Nat. Commun. 10, 592 (2019).

    Article  Google Scholar 

  29. Nakajima, M. & Yabuuchi, N. Lithium-excess cation-disordered rocksalt-type oxide with nanoscale phase segregation: Li1.25Nb0.25V0.5O2. Chem. Mater. 29, 6927–6935 (2017).

    Article  Google Scholar 

  30. Zhu, Z. et al. Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment. Nat. Energy 4, 1049–1058 (2019).

    Article  Google Scholar 

  31. Wang, Y., Yang, Z., Qian, Y., Gu, L. & Zhou, H. New insights into improving rate performance of lithium-rich cathode material. Adv. Mater. 27, 3915–3920 (2015).

    Article  Google Scholar 

  32. Shi, J.-L. et al. High-capacity cathode material with high voltage for Li-ion batteries. Adv. Mater. 30, 1705575 (2018).

    Article  Google Scholar 

  33. Li, X. et al. A new type of Li-rich rock-salt oxide Li2Ni1/3Ru2/3O3 with reversible anionic redox chemistry. Adv. Mater. 31, 1807825 (2019).

    Article  Google Scholar 

  34. Hong, J. et al. Metal–oxygen decoordination stabilizes anion redox in Li-rich oxides. Nat. Mater. 18, 256–265 (2019).

    Article  Google Scholar 

  35. Kang, K. & Ceder, G. Factors that affect Li mobility in layered lithium transition metal oxides. Phys. Rev. B 74, 94105 (2006).

    Article  Google Scholar 

  36. Sathiya, M. et al. Origin of voltage decay in high-capacity layered oxide electrodes. Nat. Mater. 14, 230–238 (2015).

    Article  Google Scholar 

  37. Bréger, J., Kang, K., Cabana, J., Ceder, G. & Grey, C. P. NMR, PDF and RMC study of the positive electrode material Li(Ni0.5Mn0.5)O2 synthesized by ion-exchange methods. J. Mater. Chem. 17, 3167–3174 (2007).

    Article  Google Scholar 

  38. Sun, X., Duffort, V., Mehdi, B. L., Browning, N. D. & Nazar, L. F. Investigation of the mechanism of Mg insertion in birnessite in nonaqueous and aqueous rechargeable Mg-ion batteries. Chem. Mater. 28, 534–542 (2016).

    Article  Google Scholar 

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

    Article  Google Scholar 

  40. Ravel, B. & Newville, M. ATHENA and ARTEMIS: interactive graphical data analysis using IFEFFIT. Phys. Scr. 15, 1007–1010 (2005).

  41. Qiao, R. et al. High-efficiency in situ resonant inelastic X-ray scattering (iRIXS) endstation at the advanced light source. Rev. Sci. Instrum. 88, 33106 (2017).

    Article  Google Scholar 

  42. Wu, J. et al. Elemental-sensitive detection of the chemistry in batteries through soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering. JoVE 134, e57415 (2018).

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

  44. Mccloskey, B. D. et al. Combining accurate O2 and Li2O2 assays to separate discharge and charge stability limitations in nonaqueous Li–O2 Batteries. J. Phys. Chem. Lett. 4, 2989–2993 (2013).

    Article  Google Scholar 

  45. McCloskey, B. D. et al. Twin problems of interfacial carbonate formation in nonaqueous Li–O2 batteries. J. Phys. Chem. Lett. 3, 997–1001 (2012).

    Article  Google Scholar 

  46. Van der Ven, A., Aydinol, M. K., Ceder, G., Kresse, G. & Hafner, J. First-principles investigation of phase stability in LixCoO2. Phys. Rev. B 58, 2975–2987 (1998).

    Article  Google Scholar 

  47. van de Walle, A. Multicomponent multisublattice alloys, nonconfigurational entropy and other additions to the Alloy Theoretic Automated Toolkit. Calphad 33, 266–278 (2009).

    Article  Google Scholar 

  48. Nelson, L. J., Hart, G. L. W., Zhou, F. & Ozoliņš, V. Compressive sensing as a paradigm for building physics models. Phys. Rev. B 87, 35125 (2013).

    Article  Google Scholar 

  49. 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 

  50. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).

    Article  Google Scholar 

  51. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Article  Google Scholar 

  52. 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 

  53. Jain, A. et al. Formation enthalpies by mixing GGA and GGA + U calculations. Phys. Rev. B 84, 45115 (2011).

    Article  Google Scholar 

  54. Reed, J., Ceder, G. & Van Der Ven, A. Layered-to-spinel phase transition in LixMnO2. Electrochem. Solid-State Lett. 4, A78 (2001).

    Article  Google Scholar 

  55. Furness, J. W., Kaplan, A. D., Ning, J., Perdew, J. P. & Sun, J. Accurate and numerically efficient r2SCAN meta-generalized gradient approximation. J. Phys. Chem. Lett. 11, 8208–8215 (2020).

    Article  Google Scholar 

  56. Sun, J., Ruzsinszky, A. & Perdew, J. P. Strongly constrained and appropriately normed semilocal density functional. Phys. Rev. Lett. 115, 36402 (2015).

    Article  Google Scholar 

  57. Kitchaev, D. A. et al. Energetics of MnO2 polymorphs in density functional theory. Phys. Rev. B 93, 45132 (2016).

    Article  Google Scholar 

  58. Henkelman, G. & Jónsson, H. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. J. Chem. Phys. 113, 9978–9985 (2000).

    Article  Google Scholar 

  59. Urban, A., Seo, D.-H. & Ceder, G. Computational understanding of Li-ion batteries. NPJ Comput. Mater. 2, 16002 (2016).

    Article  Google Scholar 

  60. Asari, Y., Suwa, Y. & Hamada, T. Formation and diffusion of vacancy-polaron complex in olivine-type LiMnPO4 and LiFePO4. Phys. Rev. B 84, 134113 (2011).

    Article  Google Scholar 

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Acknowledgements

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, under the Applied Battery Materials Program of the US Department of Energy under contract no. DE-AC02-05CH11231. The XAS measurements were performed at the Advanced Photon Source at Argonne National Laboratory, which is supported by the US Department of Energy under contract no. DE-AC02-06CH11357. Work at the Advanced Light Source was supported by the US DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231. The computational analysis was performed using computational resources sponsored by the US Department of Energy’s Office of Energy Efficiency and Renewable Energy and located at the National Renewable Energy Laboratory, as well as computational resources provided by the Extreme Science and Engineering Discovery Environment (XSEDE), supported by National Science Foundation grant no. ACI1053575, and the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility supported by the Office of Science and the US Department of Energy under contract no. DE-AC02-05CH11231. We thank H. Kim and Z. Lun for assistance with the XAS measurements.

Author information

Authors and Affiliations

  1. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Jianping Huang, Peichen Zhong, Deok-Hwang Kwon, Yaosen Tian & Gerbrand Ceder

  2. Department of Materials Science and Engineering, University of California Berkeley, Berkeley, CA, USA

    Peichen Zhong, Deok-Hwang Kwon, Yaosen Tian & Gerbrand Ceder

  3. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Yang Ha & Wanli Yang

  4. Department of Chemical and Biomolecular Engineering, University of California Berkeley, Berkeley, CA, USA

    Matthew J. Crafton & Bryan D. McCloskey

  5. Advanced Photon Source–X-ray Science Division, Argonne National Laboratory, Argonne, IL, USA

    Mahalingam Balasubramanian

  6. Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Bryan D. McCloskey

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  1. Jianping Huang
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Contributions

J.H. and G.C. planned the project. G.C. supervised all aspects of the research. J.H. synthesized, characterized and electrochemically tested the proposed materials. With help from M.B., J.H. also analysed the ex situ XAS data. P.Z. performed the theoretical calculations and analysed the results. D.-H.K. performed the TEM characterization. Y.H. collected and analysed the RIXS data with W.Y. With input from B.D.M., M.J.C. collected and analysed the DEMS data. Y.T. performed the SEM characterization. The manuscript was written by J.H. and G.C. and was revised by the other co-authors. All the authors contributed to discussions.

Corresponding author

Correspondence to Gerbrand Ceder.

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The authors declare no competing interests.

Additional information

Peer review information Nature Energy thanks Naoaki Yabuuchi, Yujie Zhu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–19, Tables 1 and 2, Notes 1–6 and references.

Source data

Source Data Fig. 1

XRD data.

Source Data Fig. 2

Electrochemical performance.

Source Data Fig. 3

XAS at Mn and Cr K-edge.

Source Data Fig. 5

XRD, electrochemistry, XAS and RIXS of LNTO and LNTC02O.

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Huang, J., Zhong, P., Ha, Y. et al. Non-topotactic reactions enable high rate capability in Li-rich cathode materials. Nat Energy 6, 706–714 (2021). https://doi.org/10.1038/s41560-021-00817-6

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