Abstract
The high volatility of the price of cobalt and the geopolitical limitations of cobalt mining have made the elimination of Co a pressing need for the automotive industry1. Owing to their high energy density and low-cost advantages, high-Ni and low-Co or Co-free (zero-Co) layered cathodes have become the most promising cathodes for next-generation lithium-ion batteries2,3. However, current high-Ni cathode materials, without exception, suffer severely from their intrinsic thermal and chemo-mechanical instabilities and insufficient cycle life. Here, by using a new compositionally complex (high-entropy) doping strategy, we successfully fabricate a high-Ni, zero-Co layered cathode that has extremely high thermal and cycling stability. Combining X-ray diffraction, transmission electron microscopy and nanotomography, we find that the cathode exhibits nearly zero volumetric change over a wide electrochemical window, resulting in greatly reduced lattice defects and local strain-induced cracks. In-situ heating experiments reveal that the thermal stability of the new cathode is significantly improved, reaching the level of the ultra-stable NMC-532. Owing to the considerably increased thermal stability and the zero volumetric change, it exhibits greatly improved capacity retention. This work, by resolving the long-standing safety and stability concerns for high-Ni, zero-Co cathode materials, offers a commercially viable cathode for safe, long-life lithium-ion batteries and a universal strategy for suppressing strain and phase transformation in intercalation electrodes.
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Data availability
Source data are provided with this paper. The data that support the findings of this study are available from the corresponding author (huolin.xin@uci.edu) upon reasonable request.
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Acknowledgements
This work is primarily supported by the US Department of Energy (DOE)’s Office of Energy Efficiency and Renewable Energy (EERE) under award no. DE-EE0008444. The in situ TEM study of Li deintercalation is supported by US DOE’s Office of Basic Energy Sciences, under award no. DE-SC0021204. The work done by R.Z. for this study was funded by the startup funding of H.L.X. R.L. was supported by the Assistant Secretary for EERE, Vehicle Technology Office of the US DOE through the Advanced Battery Materials Research (BMR) Program, under contract no. DE-SC0012704. The work performed at Pacific Northwest National Laboratory was supported by the US DOE’s Office of EERE through the Applied Battery Research Program under contract no. DE-AC05-76RL01830. This research used the resources of the Center for Functional Nanomaterials as well as 7-BM, 18-ID, 5-ID beamlines of the National Synchrotron Light Source II, which are two US DOE Office of Science facilities, at Brookhaven National Laboratory under contract no. DE-SC0012704. This research used the resources of the Advanced Photon Source, a US DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the US DOE, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515. We acknowledge the use of facilities and instrumentation at the UC Irvine Materials Research Institute, which is supported in part by the National Science Foundation through the UC Irvine Materials Research Science and Engineering Center (no. DMR-2011967). We also acknowledge the electrode produced at the US DOE’s Cell Analysis, Modeling, and Prototyping (CAMP) Facility, Argonne National Laboratory. The CAMP Facility is fully supported by the DOE Vehicle Technologies Office.
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Contributions
H.L.X. conceived the idea and directed the project. R.Z. synthesized the materials and performed the electrochemical experiments, soft/hard XAS experiments and data analysis. C.W. performed the in-situ and ex-situ TEM experiments and analyses, and TXM tomography data analyses. P.Z. performed the DSC and TGA–MS experiments. Y.R., L.Y., T.L. and Wenqian Xu performed in-situ and ex-situ XRD experiments. R.L., S.N.E. and L.M. performed the XANES and EXAFS measurements. H.J., Q.L. and Wu Xu prepared electrolytes and helped with the single-layer pouch cell test. M.G. performed the TXM experiments and data analysis. Y.Y. and A.M.K. performed the X-ray fluorescence experiments. S.S. and S.J.L. performed the soft X-ray absorption experiment. K.K. performed the FIB-SEM experiments. B.P. and S.T. fabricated the commercial NMC cathode. C.W., R.Z. and H.L.X. wrote the paper with the help of all authors.
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H.L.X. reports two US non-provisional patent applications and a PCT application filed by the University of California, Irvine, on the basis of this work.
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Extended data figures and tables
Extended Data Fig. 1 In-situ heating low-mag S/TEM and EDS mapping.
a, In-situ heating HAADF-STEM of charged HE-LNMO up to 350 °C. b, In-situ heating TEM of charged NMC-811 up to 350 °C. c, EDS mapping of charged HE-LNMO after heating at 350 °C.
Extended Data Fig. 2 Thermal stability and impedance of NMC-811 and HE-LNMO.
a, Quantified DSC result of charged state NMC-811 and HE-LNMO. Both electrodes are CC+CV charged to 4.4 V at 0.1 C current. b, EIS of LNO, NMC-811, and HE-LNMO under the same cell condition. The result shows that HE-LNMO has the lowest impedance and pure LNO has the largest impedance.
Extended Data Fig. 3 High-temperature cycling performance of NMC-811 and HE-LNMO.
a-b, Galvanostatic charge/discharge curve of HE-LNMO and NMC-811 at 50 °C, C/10. The result shows the initial Columbic efficiency of HE-LNMO (94%) is significantly higher than that of the NMC-811 (85%), indicating much less side reaction in HE-LNMO compared with NMC-811. c, cycling performance of HE-LNMO and NMC-811 at 50 °C, C/2.
Extended Data Fig. 4 FT-EXAFS of transition metals in HE-LNMO and NMC-811 before and after cycling.
a-b, FT-EXAFS of Ni, Mn before and after cycling. The TM-O bonding and TM-TM coordinate in (a) HE-LNMO and (b) NMC-811, respectively. c, FT-EXAFS of Ni, Mn, Ti, Nb and Mo in pristine HE-LNMO. d, FT-EXAFS of Ti, Nb and Mo in pristine and cycled HE-LNMO.
Extended Data Fig. 5 Multi-dimensional structural-stability characterization of NMC-811 and HE-LNMO.
a, Wavelet-transformed Ni-K edge EXAFS of HE-LNMO and NMC-811 during long-term cycling. b–c, Soft X-ray absorption (XAS) of Ni-L3 edge in cycled NMC-811 and HE-LNMO (cutoff 2.5–4.3 V, 1C) at TFY mode (b) and TEY mode (c). d–e, lattice parameters change during long cycling of (d) HE-LNMO and (e) NMC-811 calculated by XRD. f–h, X-ray fluorescence (XRF) mapping result of Ni dissolution on the graphite (Gr) anode. Ni distribution on Gr anode paired with HE-LNMO (f) and NMC-811 (g), respectively (cycling condition: 2.5V–4.4 V vs Gr, 1C; field of view: 0.25mm*0.25mm). h, Quantitative result derived from the data in f and g. i, SAED pattern of pristine HE-LNMO cathode and that after 500th long cycles. j, EDS mapping of long cycled HE-LNMO, showing the stable element distribution during long cycling.
Supplementary information
Supplementary Information
Supplementary Figs. 1–19 and Discussion. The additional characterization of HE-LNMO, cycling performance, in-situ and ex-situ cell data and the further validation of the high-entropy doping strategy’s universality are listed.
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Zhang, R., Wang, C., Zou, P. et al. Compositionally complex doping for zero-strain zero-cobalt layered cathodes. Nature 610, 67–73 (2022). https://doi.org/10.1038/s41586-022-05115-z
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DOI: https://doi.org/10.1038/s41586-022-05115-z
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