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Stalling oxygen evolution in high-voltage cathodes by lanthurization

Nature Energy volume 8, pages 159–168 (2023)Cite this article

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Abstract

Coatings and surface passivation are sought to protect high-energy-density cathodes in lithium-ion batteries, which suffer from labile oxygen loss and fast degradations. Here we develop the theory underlying the high-voltage-induced oxygen evolution crisis and report a lanthurizing process to regulate the near-surface structure of energy materials beyond conventional surface doping. Using LiCoO2 as an example and generalizing to Co-lean/free high-energy-density layered cathodes, we demonstrate effective surface passivation, suppressed surface degradation and improved electrochemical performance. High-voltage cycling stability has been greatly enhanced, up to 4.8 V versus Li+/Li, including in practical pouch-type full cells. The superior performance is rooted in the engineered surface architecture and the reliability of the synthesis method. The designed surface phase stalls oxygen evolution reaction at high voltages. It illustrates processing opportunities for surface engineering and coating by high-oxygen-activity passivation, selective chemical alloying and strain engineering using wet chemistry.

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Fig. 1: Design criteria of ideal surface coating and our solution.
Fig. 2: Surface architecture of lanthurized LCO.
Fig. 3: Gradient elements distribution at near surface of lanthurized LCO.
Fig. 4: Superior electrochemical performance of La-LCO over P-LCO.
Fig. 5: Full-cell performance of La-LCO and P-LCO.
Fig. 6: La-LCO with stabilized surface oxygen and oxygen storage surface phase.

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Data supporting the findings in the present work are available in the manuscript and supplementary information.

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Acknowledgements

F.H. acknowledges support by the National Natural Science Foundation of China (grants 21871008, 11227902), the Science and Technology Commission of Shanghai (grant 18YF1427200) and the Key Research Program of Frontier Science, Chinese Academy of Sciences (grant number QYZDJ-SSW-JSC013). J.L. acknowledges support from Samsung Advanced Institute of Technology. We thank beamline 02B02 of the Shanghai Synchrotron Radiation Facility for providing the beamtime.

Author information

Author notes

  1. These authors contributed equally: Mingzhi Cai, Yanhao Dong.

Authors and Affiliations

  1. College of Chemistry and Molecular Engineering, Peking University, Beijing, China

    Mingzhi Cai, Yunsong Ge & Fuqiang Huang

  2. Department of Nuclear Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA

    Yanhao Dong, Moonsu Yoon, Haowei Xu & Ju Li

  3. State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing, China

    Yanhao Dong

  4. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, China

    Miao Xie, Wujie Dong, Xuzhou Sun, Shaoning Zhang & Fuqiang Huang

  5. School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, China

    Chenlong Dong

  6. College of Chemistry and Chemical Engineering and College of Energy and School of Energy Research, Xiamen University, Xiamen, China

    Peng Dai

  7. Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai, China

    Hui Zhang

  8. College of Chemistry, Zhengzhou University, Zhengzhou, China

    Xin Wang

  9. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA

    Ju Li

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  1. Mingzhi Cai
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Contributions

F.H. conceived the project. J.L. developed the theory. M.C. and F.H. synthesized the materials and conducted the electrochemical measurements. Y.D. and H.X. conducted the simulations. M.C. and M.X. assembled and tested pouch-type full cells. P.D. conducted in situ DEMS measurements. H.Z. conducted sXAS measurements. S.Z. conducted XPS depth profile measurements. M.C., Y.D. and F.H. analysed the data. M.C., Y.D., J.L. and F.H. wrote the paper. All authors discussed and contributed to the writing.

Corresponding authors

Correspondence to Ju Li or Fuqiang Huang.

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Extended data

Extended Data Fig. 1 Post-cycling morphological, structural and chemical characteristics of oxide surface and CEIs.

a, b, HRTEM near the surface of cycled P-LCO (a) and La-LCO (b). Circled in (a) are Moire effects produced by lattice distortion. c, d, Depth-resolved EELS profiles near the surface of cycled P-LCO (c) and La-LCO (d). e, f, Calculated Co L3/L2 area ratio (e) and O/Co ratio (f) of cycled P-LCO and La-LCO from (c, d). g, h, HRTEM near the surfaces of cycled P-LCO (g) and La-LCO (h), showing the CEI layer enclosed by dash lines. Scale bars: 5 nm (a, b, g, h). i–l, XPS of C 1s (i, k) and F 1s (j, l) for cycled P-LCO (i, j) and La-LCO (k, l). Details for XPS analysis are listed in Supplementary Table 5 and 6. Characterizations in (a–l) were conducted on samples after 100 cycles at 1 C and 3.0–4.6 V (vs. Li+/Li) in half cells. m, Dissolved Co in the electrolytes after 100 and 200 cycles under 1 C within 3.0–4.6 V (vs. Li+/Li) in half cells. n, o, XPS of Co 2p at the surface of the cycled graphite anodes in pouch cells using La-LCO (n) and P-LCO (o) cathodes after 200 cycles under 200 mA at full-cell voltages 3.0–4.5 V.

Extended Data Fig. 2 Generalization of lanthurizing process to Co-lean NCM and Co-free LRNM cathodes.

a, Cycling performance of P-NCM and La-NCM in coin-type half cells at 1 C at 2.8–4.4 V vs. Li+/Li. b, c, Charge–discharge profiles of P-NCM (b) and La-NCM (c) at the 5th, 50th, 100th and 150th cycles. d, Cycling performance of P-LRNM and La-LRNM in coin-type half cells at 1 C at 2.0–4.8 V vs. Li+/Li. e, f, Charge–discharge profiles of P-LRNM (e) and La-LRNM (f) at the 5th, 50th, 100th and 150th cycles.

Supplementary information

Supplementary Information

Supplementary Notes 1–3, Figs. 1–24, Tables 1–9 and References.

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Cai, M., Dong, Y., Xie, M. et al. Stalling oxygen evolution in high-voltage cathodes by lanthurization. Nat Energy 8, 159–168 (2023). https://doi.org/10.1038/s41560-022-01179-3

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