Abstract
Layered transition metal oxide cathodes (NaxTMO2) demonstrate a classic type of cathode for Sodium-ion batteries (SIBs), however their practical application faces a long-standing challenge of irreversible phase transitions at high voltages, which causes unsatisfied specific energy and cycling stability, particularly for P-type (Na+ located at prismatic sites) cathodes. This phenomenon is conventionally ascribed to the Na+ re-coordination from prismatic to octahedral (O-type) configuration upon Na+ extraction, whereby the TMO2 slab gliding and abrupt c-lattice change are always coupled, and a straightforward solution to this situation remains elusive. Here, we reveal that, the TMO2 slab gliding and the lattice contraction can be decoupled, and the rapid lattice contraction under high state-of-charge underlies the fundamental origin for the irreversible phase transitions. By pre-engineering 15.8% O-type stacking faults to a P-type Na0.7Mn0.8Ni0.2O2, the dramatic volume variation and irreversible phase transitions at high voltage (4.5 V vs. Na+/Na) can be primarily eliminated. This work advances the understanding on the phase transitions at deep desodiation states, and paves up a feasible way to realize high-energy layered oxides.
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Acknowledgements
This work is supported by the National Natural Science Foundation of China (22479091, 22179077), and East China Normal University Multifunctional Platform for Innovation (004). We greatly appreciate the neutron beamtime granted from the China Spallation Neutron Source (CSNS) and the technical assistance from Huaican Chen. We greatly appreciate for the beamline time given by BL14B1 for testing X-ray diffraction, and BL14W1 station for testing X-ray absorption spectroscopy from the Shanghai Synchrotron Radiation Facility (SSRF). This work is supported by the Shanghai Technical Service Center of Science and Engineering Computing, Shanghai University. The three-dimensional visualization of crystal, volumetric data of this study, was performed using VESTA software (Version 3). We acknowledge the development team of this software, and its use is supported by the following reference: K. Momma and F. Izumi, “VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data,” J. Appl. Crystallogr., 44, 1272-1276 (2011).
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Y.-F.Z. and J.L. conceived and planned the project concept. J.L. and Y.-F.Z. supervised the project. Q.-H.S. performed experiments and initial data analysis. F.-H.N., X.Y., and Z.-P.Y. carried out the theoretical calculation analysis. F.-J.X., R.-J.Q., and J.-S.W. carried out STEM measurements. G.-F.C. carried out XRD test and calculated stacking faults probability. Y.Q. and H.-Y.L. carried out electrochemical tests. H.-F.Z. analyzed XRD and STEM results. T.Z. performed the DEMS test. S.-G.L. and T.L. carried out pouch cell fabrication. Y.-C.L. conducted PDF measurements. H.-C.C. carried out the NPD test. W.W. performed synchrotron XRD tests. Q.-H.S. wrote the original draft. J.-J.Z. reviewed and edited the manuscript. All authors discussed the results, co-wrote and commented on the paper.
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Shi, Q., Ning, F., Yu, X. et al. Decoupling slab gliding and lattice contraction in Na layered oxides to enable high-voltage Na-ion batteries. Nat Commun (2026). https://doi.org/10.1038/s41467-025-68238-7
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DOI: https://doi.org/10.1038/s41467-025-68238-7
