Surfaces, interfaces and grain boundaries are classically known to be sinks of defects generated within the bulk lattice. Here, we report an inverse case by which the defects generated at the particle surface are continuously pumped into the bulk lattice. We show that, during operation of a rechargeable battery, oxygen vacancies produced at the surfaces of lithium-rich layered cathode particles migrate towards the inside lattice. This process is associated with a high cutoff voltage at which an anionic redox process is activated. First-principle calculations reveal that triggering of this redox process leads to a sharp decrease of both the formation energy of oxygen vacancies and the migration barrier of oxidized oxide ions, therefore enabling the migration of oxygen vacancies into the bulk lattice of the cathode. This work unveils a coupled redox dynamic that needs to be taken into account when designing high-capacity layered cathode materials for high-voltage lithium-ion batteries.
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Data that support the findings of this study are kept at the William R. Wiley Environmental Molecular Sciences Laboratory at PNNL and are available from the corresponding authors upon request.
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This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies, of the US Department of Energy (DOE) under contract no. DE-AC02-05CH11231, subcontract no. 6951379 under the Batteries for Advanced Battery Materials Research. The work was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at PNNL. PNNL is operated by Battelle for DOE under contract DE-AC05-76RLO1830. L.-M.L. was supported by the Science Challenge Project (TZ2018004) of the National Natural Science Foundation of China (nos. 51572016 and U1530401) and the Fundamental Research Funds for the Central Universities, and Newton Advanced Fellowship under grant no. NAFR1180242. P.Y. acknowledges support from the National Natural Science Fund for Innovative Research Groups (grant no. 51621003) and the National Key Research and Development Program of China (grant no. 2016YFB0700700). Z.-K.T. thanks the National Natural Science Foundation of China (grant no. 51602092) for support.
The authors declare no competing interests.
Journal peer review information: Nature Nanotechnology thanks Jun Chen and the other anonymous reviewer(s) for their contribution to the peer review of this work.
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Yan, P., Zheng, J., Tang, ZK. et al. Injection of oxygen vacancies in the bulk lattice of layered cathodes. Nat. Nanotechnol. 14, 602–608 (2019). https://doi.org/10.1038/s41565-019-0428-8
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