Lithium-rich layered oxides (LRLO) are among the leading candidates for the next-generation cathode material for energy storage, delivering 50% excess capacity over commercially used compounds. Despite excellent prospects, voltage fade has prevented effective use of the excess capacity, and a major challenge has been a lack of understanding of the mechanisms underpinning the voltage fade. Here, using operando three-dimensional Bragg coherent diffractive imaging, we directly observe the nucleation of a mobile dislocation network in LRLO nanoparticles. The dislocations form more readily in LRLO as compared with a classical layered oxide, suggesting a link between the defects and voltage fade. We show microscopically how the formation of partial dislocations contributes to the voltage fade. The insights allow us to design and demonstrate an effective method to recover the original high-voltage functionality. Our findings reveal that the voltage fade in LRLO is reversible and call for new paradigms for improved design of oxygen-redox active materials.
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We acknowledge K. Wiaderek for providing the potentiostat during the measurements at the Advanced Photon Source and H. Liu and K. Chapman for collecting the ex situ powder diffraction data on the NCA material. We also thank A. Van der Ven and M. Radin for discussions. The X-ray imaging was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, under contract DE-SC0001805 (A.S., D.C., J.W., N.H. and O.G.S.). S.H., C.F., M.Z., H.L. and Y.S.M. acknowledge support on the materials synthesis, electrochemical and materials characterization from the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award no. DE-SC0012583. The sample exchanges and collaborations between UCSD and NIMTE are made possible with the support from Office of Vehicle Technology of the U.S. DOE under the Advanced Battery Materials Research (BMR) Program. This research used resources of the Advanced Photon Source, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. We thank the staff at Argonne National Laboratory and the Advanced Photon Source for their support. Parts of this research were carried out at the light source PETRA III at DESY, a member of the Helmholtz Association (HGF). The data are stored at Sector 34-ID-C of the Advanced Photon Source and at PETRA III at DESY.
The authors declare no competing interests.
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Supplementary Figures 1–15 and Supplementary Table 1
A 3D representation of the displacement field inside the nanoparticle at 4.0 V state of charge. False colours as in Fig. 2a
A 3D representation of the displacement field inside the nanoparticle at 4.3 V state of charge. False colours as in Fig. 2a
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Singer, A., Zhang, M., Hy, S. et al. Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging. Nat Energy 3, 641–647 (2018). https://doi.org/10.1038/s41560-018-0184-2
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