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Approaching the capacity limit of lithium cobalt oxide in lithium ion batteries via lanthanum and aluminium doping

Abstract

Lithium cobalt oxides (LiCoO2) possess a high theoretical specific capacity of 274 mAh g–1. However, cycling LiCoO2-based batteries to voltages greater than 4.35 V versus Li/Li+ causes significant structural instability and severe capacity fade. Consequently, commercial LiCoO2 exhibits a maximum capacity of only ~165 mAh g–1. Here, we develop a doping technique to tackle this long-standing issue of instability and thus increase the capacity of LiCoO2. La and Al are concurrently doped into Co-containing precursors, followed by high-temperature calcination with lithium carbonate. The dopants are found to reside in the crystal lattice of LiCoO2, where La works as a pillar to increase the c axis distance and Al as a positively charged centre, facilitating Li+ diffusion, stabilizing the structure and suppressing the phase transition during cycling, even at a high cut-off voltage of 4.5 V. This doped LiCoO2 displays an exceptionally high capacity of 190 mAh g–1, cyclability with 96% capacity retention over 50 cycles and significantly enhanced rate capability.

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Acknowledgements

We gratefully acknowledge the support from the US Department of Energy’s (DOE) Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. Use of the Advanced Photon Source and the Centre for Nanoscale Materials, Office of Science user facilities operated for DOE, Office of Science by Argonne National Laboratory, was supported by the US DOE under contract no. DE-AC02-06CH11357. The authors acknowledge H. Zhou, X. Zhang, Y. Liu, C.-J. Sun and S. Lapidus for help and discussion with the synchrotron experiments and STEM data. We thank M.-L. Saboungi and D. Price for critical reading of the manuscript.

Author information

Y.L. and W.L. conceived the idea. Q.L., X.S. and D.L. designed and performed the experiments. X.S., Q.L. and Y.Q. performed the electrochemical characterization. Q.L., X.S., Y.Ro., F.G., R.K., X.X. and Y.Re. carried out the in situ and ex situ synchrotron measurements. Q.L., Y.Ro. and Y.Re. analysed and interpreted the synchrotron XRD data. D.L. and X.S. performed the SEM work. J.W., D.L. and Y.W. acquired the STEM and HAADF images. F.A. and J.B. contributed to discussions and interpretation of the electrochemical data. Q.L., D.L., X.S., Y.Re., W.L. and Y.L. wrote the paper. The project was supervised by Y.L., W.L. and Y.Re. All authors discussed the results and reviewed the manuscript.

Correspondence to Xin Su or Yang Ren or Yangxing Li.

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Further reading

Fig. 1: Ex situ characterization of D-LCO and P-LCO.
Fig. 2: Electrochemical characterization of P-LCO and D-LCO.
Fig. 3: In situ synchrotron HEXRD characterization for D-LCO during the first charge–discharge process.
Fig. 4: Li ion diffusion coefficient determination of P-LCO and D-LCO via GITT.
Fig. 5: ASI data of P-LCO and D-LCO determined via HPPC.
Fig. 6: SEM characterization of P-LCO and D-LCO particles after the cycling test.