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A high-energy-density and long-life initial-anode-free lithium battery enabled by a Li2O sacrificial agent

Nature Energy volume 6, pages 653–662 (2021)Cite this article

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Abstract

Equipped with a fully lithiated cathode with a bare anode current collector, the anode-free lithium cell architecture presents remarkable advantages in terms of both energy density and safety compared with conventional lithium-ion cells. However, it is challenging to realize high Li reversibility, especially considering the limited Li reservoir (typically zero lithium excess) in the cell configuration. In this study we have introduced Li2O as a preloaded sacrificial agent on a LiNi0.8Co0.1Mn0.1O2 cathode, providing an additional Li source to offset the irreversible loss of Li during long-term cycling in an initial-anode-free cell. We show that O2− species, released through Li2O oxidation, are synergistically neutralized by a fluorinated ether additive. This leads to the construction of a LiF-based layer at the cathode/electrolyte interface, which passivates the cathode surface and restrains the detrimental oxidative decomposition of ether solvents. We have achieved a long-life 2.46 Ah initial-anode-free pouch cell with a gravimetric energy density of 320 Wh kg–1, maintaining 80% capacity after 300 cycles.

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Fig. 1: Cathode and electrolyte design strategies for the anode-free Li cell system.
Fig. 2: Evaluation of Li-metal plating/stripping reversibility and initial-anode-free full-cell cycling performance in a coin cell.
Fig. 3: Characterization of the NCM@Li2O cathode in the initial precharging process.
Fig. 4: Proposed mechanism for the construction of the LiF cathode surface protective layer by the synergy between the HFE additive and oxidized Li2O.
Fig. 5: Performance of 320 Wh kg–1 initial-anode-free Li pouch cells.

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Source data are provided with this paper. All other data generated during this study are included in the published article and its Supplementary Information.

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Acknowledgements

We thank L. Pan (Hokkaido University, Japan) for his help in the Raman and DEMS characterizations and general discussion.

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Author notes

  1. Yu Qiao

    Present address: College of Chemistry and Chemical Engineering, Xiamen University, Fujian, China

Authors and Affiliations

  1. Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology, Tsukuba, Japan

    Yu Qiao, Huijun Yang, Zhi Chang, Han Deng, Xiang Li & Haoshen Zhou

  2. Center of Energy Storage Materials and Technology, College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid State Microstructures and Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, China

    Haoshen Zhou

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Contributions

Y.Q. and H.Z. contributed to the design of the research and analysed the experimental data. Y.Q. conducted the electrochemical and spectroscopic characterizations. H.Y. prepared the electrolyte and studied the anode performance. Z.C. performed the SEM and TEM characterizations. X.L. conducted the XRD characterization and refinement. H.D. prepared Li2O. H.Z. supervised the work. All the authors discussed the results, co-wrote the manuscript and commented on the manuscript.

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Correspondence to Haoshen Zhou.

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Peer review information Nature Energy thanks Michael Metzger and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

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Qiao, Y., Yang, H., Chang, Z. et al. A high-energy-density and long-life initial-anode-free lithium battery enabled by a Li2O sacrificial agent. Nat Energy 6, 653–662 (2021). https://doi.org/10.1038/s41560-021-00839-0

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