Abstract
High-nickel layered positive electrodes suffer from progressive structural degradation arising from lattice oxygen loss and inherent lattice strain. Although surface coatings are widely used to stabilize lattice-oxygen redox and mitigate electro-chemo-mechanical degradation, achieving coatings with full continuity, robust interfacial bonding, and fast Li+ conductivity remains challenging. Herein, we present a fundamentally different approach to shell formation via a self-derived subtractive strategy, departing from the conventional additive-based coating methods. By accurately applying transient thermal pulses, surface lithium is selectively extracted from layered LiNixCoyMn1-x-yO2 (x = 0.8 ~ 0.9), directly converting the outer region into a coherent spinel-phase shell with tunable thickness. This nanoscale spinel-phase skin forms a robust mortise-and-tenon-like interconnection with the layered bulk, enabling isotropic, high-rate Li+ extraction/insertion while maintaining electronic conductivity throughout cycling. It effectively confines active oxygen intermediates, and suppresses interfacial side reactions and strain evolution under high-potential operation. Therefore, the spinel-phase skin-encapsulated LiNi0.8Co0.1Mn0.1O2 achieves an initial Coulombic efficiency of 95.3% and enables pouch cells with 80.1% capacity retention after 2000 cycles at 180 mA g-1. This strategy is extendable to LiNi0.9Co0.05Mn0.05O2, may open new avenues for advancing nickel-rich positive electrode technologies.
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All data generated or analyzed during this study are included in the published article and its Supplementary Information. Additional data are available from the corresponding authors on request. Source data are provided with this paper.
References
Li, W., Erickson, E. M. & Manthiram, A. High-nickel layered oxide cathodes for lithium-based automotive batteries. Nat. Energy 5, 26–34 (2020).
Liu, J. et al. Pathways for practical high-energy long-cycling lithium metal batteries. Nat. Energy 4, 180–186 (2019).
Xu, C. et al. Bulk fatigue induced by surface reconstruction in layered Ni-rich cathodes for Li-ion batteries. Nat. Mater. 20, 84–92 (2021).
Jiao, S., Wang, J., Hu, Y.-S., Yu, X. & Li, H. High-capacity oxide cathode beyond 300 mAh/g. ACS Energy Lett. 8, 3025–3037 (2023).
Ryu, H.-H., Park, K.-J., Yoon, C. S. & Sun, Y.-K. Capacity fading of Ni-Rich Li[NixCoyMn1–x–y]O2 (0.6≤x≤0.95) cathodes for high-energy-density lithium-ion batteries: bulk or surface degradation? Chem. Mater. 30, 1155–1163 (2018).
Yan, P. et al. Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries. Nat. Commun. 8, 14101 (2017).
Lin, F. et al. Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries. Nat. Commun. 5, 3529 (2014).
Li, W., Asl, H. Y., Xie, Q. & Manthiram, A. Collapse of LiNi1-x-yCoxMnyO2 lattice at deep charge irrespective of nickel content in lithium-ion batteries. J. Am. Chem. Soc. 141, 5097–5101 (2019).
Li, S. et al. Mutual modulation between surface chemistry and bulk microstructure within secondary particles of nickel-rich layered oxides. Nat. Commun. 11, 4433 (2020).
Wang, L. et al. Reaction inhomogeneity coupling with metal rearrangement triggers electrochemical degradation in lithium-rich layered cathode. Nat. Commun. 12, 5370 (2021).
Xu, C. et al. Operando visualization of kinetically induced lithium heterogeneities in single-particle layered Ni-rich cathodes. Joule 6, 2535–2546 (2022).
Yu, R. et al. Layer-by-layer delithiation during lattice collapse as the origin of planar gliding and microcracking in Ni-rich cathodes. Cell Rep. Phys. Sci. 4, 101480 (2023).
Lin, F., Zhao, K. & Liu, Y. Heterogeneous reaction activities and statistical characteristics of particle cracking in battery electrodes. ACS Energy Lett. 6, 4065–4070 (2021).
Wei, Z. et al. In-depth study on diffusion of oxygen vacancies in Li(NixCoyMnz)O2 cathode materials under thermal induction. Energy Storage Mater. 47, 51–60 (2022).
Meng, X.-H. et al. Kinetic origin of planar gliding in single-crystalline Ni-rich cathodes. J. Am. Chem. Soc. 144, 11338–11347 (2022).
Li, J. et al. Dynamics of particle network in composite battery cathodes. Science 376, 517–521 (2022).
Zhao, C. et al. Suppressing strain propagation in ultrahigh-Ni cathodes during fast charging via epitaxial entropy-assisted coating. Nat. Energy 9, 345–356 (2024).
Lu, S.-Q. et al. Surface lattice modulation through chemical delithiation toward a stable nickel-rich layered oxide cathode. J. Am. Chem. Soc. 145, 7397–7407 (2023).
Cheng, J. et al. Improving intrinsic safety of Ni-rich layered oxide cathode by modulating its electronic surface state. Energy Storage Mater. 79, 104332 (2025).
Wang, R. et al. Inhibiting phase conversion and improving cyclic stability of Ni-rich layered oxide by high-valence element concentration gradient doping. Chem. Eng. J. 485, 149827 (2024).
Wang, L., Liu, T., Wu, T. & Lu, J. Strain-retardant coherent perovskite phase stabilized Ni-rich cathode. Nature 611, 61–67 (2022).
Ryu, H.-H., Lim, H.-W., Lee, S. G. & Sun, Y.-K. Near-surface reconstruction in Ni-rich layered cathodes for high-performance lithium-ion batteries. Nat. Energy 9, 47–56 (2024).
Liu, W. et al. Functional passivation interface of LiNi0.8Co0.1Mn0.1O2 toward superior lithium storage. Adv. Funct. Mater. 31, 2008301 (2021).
Yoon, M. et al. Reactive boride infusion stabilizes Ni-rich cathodes for lithium-ion batteries. Nat. Energy 6, 362–371 (2021).
Guo, W. et al. In situ surface engineering enables high interface stability and rapid reaction kinetics for Ni-rich cathodes. eScience 3, 100082 (2023).
Tian, Y. et al. Regulation of interface ion transport by electron ionic conductor construction toward high-voltage and high-rate LiNi0.5Co0.2Mn0.3O2 cathodes in lithium ion battery. Adv. Sci. 11, 2402380 (2024).
Yao, J. et al. Scalable precise nanofilm coating and gradient al doping enable stable battery cycling of LiCoO2 at 4.7 V. Angew. Chem. Int. Ed. Engl. 63, e202407898 (2024).
Guo, H.-J. et al. Surface degradation of single-crystalline Ni-rich cathode and regulation mechanism by atomic layer deposition in solid-state lithium batteries. Angew. Chem. Int. Ed. Engl. 61, e202211626 (2022).
Zhang, C. et al. Quenching-etched surface spinel to passivate layered cathode materials from structural degradation at high potentials. Chem. Mater. 35, 6692–6701 (2023).
Gan, Q. et al. Surface spinel reconstruction to suppress detrimental phase transition for stable LiNi0.8Co0.1Mn0.1O2 cathodes. Nano. Res. 16, 513–520 (2023).
Wang, K. et al. Unraveling the role of surficial oxygen vacancies in stabilizing Li-rich layered oxides. Adv. Energy Mater. 13, 2301216 (2023).
Qi, S. et al. A pre-fatigue training strategy to stabilize LiCoO2 at high voltage. Energy Environ. Sci. 17, 2269–2278 (2024).
Cheng, X. et al. Pre-deoxidation of layered Ni-rich cathodes to construct a stable interface with electrolyte for long cycling life. Adv. Funct. Mater. 33, 2211171 (2023).
Hao, Z. et al. Suppressing bulk strain and surface O2 release in Li-rich cathodes by just tuning the Li content. Adv. Mater. 36, 2307617 (2024).
Liang, C. et al. Insight into the structural evolution and thermal behavior of LiNi0.8Co0.1Mn0.1O2 cathode under deep charge. J. Energy Chem. 65, 424–432 (2022).
Lee, S.-B. et al. Doping strategy in developing Ni-rich cathodes for high-performance lithium-ion batteries. ACS Energy Lett. 9, 740–747 (2024).
Xu, C., Reeves, P. J., Jacquet, Q. & Grey, C. P. Phase behavior during electrochemical cycling of Ni-rich cathode materials for Li-ion batteries. Adv. Energy Mater. 11, 2003404 (2021).
Liu, X. et al. Origin and regulation of oxygen redox instability in high-voltage battery cathodes. Nat. Energy 7, 808–817 (2022).
Wang, W. et al. Optimized in situ doping strategy stabling single-crystal ultrahigh-nickel layered cathode materials. ACS Nano 18, 8002–8016 (2024).
Dai, Z., Li, Z., Chen, R., Wu, F. & Li, L. Defective oxygen inert phase stabilized high-voltage nickel-rich cathode for high-energy lithium-ion batteries. Nat. Commun. 14, 8087 (2023).
Shi, X. et al. Achieving high safety for lithium-ion batteries by optimizing electron and phonon transport. ACS Energy Lett. 8, 4540–4546 (2023).
Zhang, B. et al. Manipulated fluoro-ether derived nucleophilic decomposition products for mitigating polarization-induced capacity loss in Li-rich layered cathode. Angew. Chem. Int. Ed. Engl. 63, e202316790 (2024).
Zhuang, Z. et al. Ultrahigh-Voltage LiCO2 at 4.7 V by interface stabilization and band structure modification. Adv. Mater. 35, 2212059 (2023).
Ryu, H.-H., Lim, H.-W., Kang, G.-C., Park, N.-Y. & Sun, Y.-K. Long-lasting Ni-rich NCMA cathodes via simultaneous microstructural refinement and surface modification. ACS Energy Lett. 8, 1354–1361 (2023).
Zhang, R. et al. Compositionally complex doping for zero-strain zero-cobalt layered cathodes. Nature 610, 67–75 (2022).
Zhang, R. et al. Long-life lithium-ion batteries realized by low-Ni, Co-free cathode chemistry. Nat. Energy 8, 695–702 (2023).
Wang, Z. et al. Contact-electro-catalysis for the degradation of organic pollutants using pristine dielectric powders. Nat. Commun. 13, 130 (2022).
Momma, K. & Izumi, F. VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Cryst. 44, 1272–1276 (2011).
Kang, K., Morgan, D. & Ceder, G. First principles study of Li diffusion in I-Li2NiO2 structure. Phys. Rev. B 79, 014305 (2009).
Zhou, Z. et al. First-Principles study on the interplay of strain and state-of-charge with Li-ion diffusion in the battery cathode material LiCoO2. ACS Appl. Mater. Interfaces 15, 53614–53622 (2023).
Kresse, G. Ab initio molecular dynamics for liquid metals. J. Non-Cryst. Solids 192, 222–229 (1995).
Kresse, G. & Hafner, J. Ab initiomolecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251–14269 (1994).
Kresse, G. & Furthmuller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
Kresse, G. & Furthmuller, 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).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Olsson, E., Chai, G., Dove, M. & Cai, Q. Adsorption and migration of alkali metals (Li, Na, and K) on pristine and defective graphene surfaces. Nanoscale 11, 5274–5284 (2019).
Wang, Z. et al. In-situ formed Co nano-clusters as separator modifier and catalyst to regulate the film-like growth of Li and promote the cycling stability of lithium metal batteries. J. Colloid Interface Sci. 660, 226–234 (2024).
Behler, J. Atom-centered symmetry functions for constructing high-dimensional neural network potentials. J. Chem. Phys. 134, 074106 (2011).
Zhou, Z. et al. Tuning the electronic, ion transport, and stability properties of Li-rich manganese-based oxide materials with oxide perovskite coatings: A first-principles computational study. ACS Appl. Mater. Interfaces 14, 37009–37018 (2022).
Zhou, Z. et al. LiNbO3 and LiTaO3 coating effects on the interface of the LiCoO2 cathode: A DFT study of Li-ion transport. ACS Appl. Mater. Interfaces 16, 42093–42099 (2024).
Van de Walle, A. et al. Efficient stochastic generation of special quasirandom structures. Calphad 42, 13–18 (2013).
Acknowledgements
This work was supported by the National Natural Science Foundation of China (Grant Nos. 92372101-L.Z., U25A20237-Q.Z., 92472104-Q.Z., 92472203-L.Z.), National Key Research and Development Program of China (grant 2024YFE0209300-Q.Z.), the Fundamental Research Funds for the Central Universities (20720220010-L.Z., 20720230036-J.H.), the National Key Research and Development Program of China (2021YFA1201502-L.Z.), Fujian Provincial Natural Science Foundation of China (2024J01038-J.H.). L. Zhang and Q.B. Zhang acknowledge the support of Nanqiang Young Top-notch Talent Fellowship in Xiamen University. H.P. Yang, Z.F. Sun and Y.H. Zhao contribute equally to this work.
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L. Zhang and Q.B. Zhang conceived the idea and supervised the experiments. H.P. Yang and Y.H. Zhao synthesized the materials and wrote the paper. Z.F. Sun conducted the HRTEM experiments and electrochemical testing. Z.Y. Sun and W.X. Chen conducted the XANES experiments. H.L. Yi, Y. Zhang and J.J. Liu conducted the TOF-SIMS and XPS experiments. H.Q. Wang and Y.X. Mao conducted the in situ XRD and SEM experiments. J.J. Han conducted the theoretical calculations. J.X. Wang, Q.H. Zhao, S.J. Feng and Y. Cao assisted in revising the paper. All the authors discussed and commented on the manuscript.
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Yang, H., Sun, Z., Zhao, Y. et al. Flash joule heating-induced spinel-phase surface in Ni-rich layered oxide positive electrodes to stabilise lattice oxygen. Nat Commun (2026). https://doi.org/10.1038/s41467-026-70616-8
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DOI: https://doi.org/10.1038/s41467-026-70616-8
