Ultrahigh power and energy density in partially ordered lithium-ion cathode materials

Abstract

The rapid market growth of rechargeable batteries requires electrode materials that combine high power and energy and are made from earth-abundant elements. Here we show that combining a partial spinel-like cation order and substantial lithium excess enables both dense and fast energy storage. Cation overstoichiometry and the resulting partial order is used to eliminate the phase transitions typical of ordered spinels and enable a larger practical capacity, while lithium excess is synergistically used with fluorine substitution to create a high lithium mobility. With this strategy, we achieved specific energies greater than 1,100 Wh kg–1 and discharge rates up to 20 A g–1. Remarkably, the cathode materials thus obtained from inexpensive manganese present a rare case wherein an excellent rate capability coexists with a reversible oxygen redox activity. Our work shows the potential for designing cathode materials in the vast space between fully ordered and disordered compounds.

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Fig. 1: Structural and morphological characterization of two oxyfluorides LMOF03 and LMOF06.
Fig. 2: Galvanostatic charge and discharge performance of LMOF03 and LMOF06 at 50 mA g–1 at room temperature.
Fig. 3: Redox mechanism of LMOF03.
Fig. 4: Rate capability measurements.
Fig. 5: Illustration of partially (dis)ordered cation and anion local environments in a spinel-like structure that arise from Li overstoichiometry and substitution.

Data availability

The datasets generated and analysed during the current study are available from the corresponding author upon reasonable request.

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Acknowledgements

This work is supported by the Umicore Specialty Oxides and Chemicals and the Assistant Secretary of Energy Efficiency and Renewable Energy, Vehicle Technologies Office of the US Department of Energy (DOE) under contract no. DE-AC02-05CH11231 under the Advanced Battery Materials Research (BMR) Program. Recent characterization 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 DOE under contract no. DE-AC02-05CH11231. Work at the Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US DOE under contract no. DE-AC02-05CH11231. Research conducted at the Nanoscale Ordered Materials Diffractometer Beamline at Oak Ridge National Laboratory’s Spallation Neutron Source is sponsored by the Scientific User Facilities Division, Office of Basic Sciences of the US DOE. Work at the Molecular Foundry at Lawrence Berkeley National Laboratory is supported by the Office of Science, Office of Basic Energy Sciences of the US DOE under contract no. DE-AC02-05CH11231. This research used resources of the Advanced Photon Source, an Office of Science User Facility operated for the US DOE Office of Science by Argonne National Laboratory, and is supported by the US DOE under contract no. DE-AC02-06CH11357. The NMR experimental work reported here made use of the shared facilities of the UCSB MRSEC (NSF DMR 1720256), a member of the Material Research Facilities Network. H.J. acknowledges support from the Assistant Secretary of Energy Efficiency and Renewable Energy, Vehicle Technologies Office of the US DOE, under contract no. DE-AC02-05CH11231. J.K.P. also acknowledges support from the NSF Graduate Research Fellowship under contract no. DGE-1106400.

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H.J. and G.C. planned the project. G.C. supervised all aspects of the research. H.J. designed the proposed compounds. H.J. and Z.C. synthesized and electrochemically tested the compounds with help from H.K. J.W. performed the mRIXS measurements and analysed the data with input from W.Y. J.L. performed the neutron diffraction measurements and analysed the neutron and synchrotron diffraction data. D.-H.K. acquired and analysed the transmission electron microscopy, electron diffraction and EDS data. H.K. collected the operando XANES data with help from M.B. and Z.C. A.U. performed computational percolation analysis. J.K.P. acquired and analysed the differential electrochemical mass spectrometer data with input from B.D.M. E.F. acquired and analysed the NMR data with input from R.J.C. Y.T. collected SEM and synchrotron diffraction data. The manuscript was written by H.J. and G.C. and revised by A.U., J.W. and J.L. with the help from other authors.

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Correspondence to Gerbrand Ceder.

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Supplementary Notes 1–5, Figs. 1–19, Tables 1–8 and refs. 1–8.

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Ji, H., Wu, J., Cai, Z. et al. Ultrahigh power and energy density in partially ordered lithium-ion cathode materials. Nat Energy 5, 213–221 (2020). https://doi.org/10.1038/s41560-020-0573-1

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