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Raising the cycling stability of aqueous lithium-ion batteries by eliminating oxygen in the electrolyte

Nature Chemistry volume 2, pages 760–765 (2010)Cite this article

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Abstract

Aqueous lithium-ion batteries may solve the safety problem associated with lithium-ion batteries that use highly toxic and flammable organic solvents, and the poor cycling life associated with commercialized aqueous rechargeable batteries such as lead-acid and nickel-metal hydride systems. But all reported aqueous lithium-ion battery systems have shown poor stability: the capacity retention is typically less than 50% after 100 cycles. Here, the stability of electrode materials in an aqueous electrolyte was extensively analysed. The negative electrodes of aqueous lithium-ion batteries in a discharged state can react with water and oxygen, resulting in capacity fading upon cycling. By eliminating oxygen, adjusting the pH values of the electrolyte and using carbon-coated electrode materials, LiTi2(PO4)3/Li2SO4/LiFePO4 aqueous lithium-ion batteries exhibited excellent stability with capacity retention over 90% after 1,000 cycles when being fully charged/discharged in 10 minutes and 85% after 50 cycles even at a very low current rate of 8 hours for a full charge/discharge offering an energy storage system with high safety, low cost, long cycling life and appropriate energy density.

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Figure 1: The intercalation potential of some electrode materials that could possibly be used for aqueous lithium-ion batteries.
Figure 2: Cyclic voltammograms of LiTi2(PO4)3 at the 1st, 2nd, 3rd, 5th and 10th cycles.
Figure 3: Typical charge/discharge curves of LiTi2(PO4)3 at 4C and 1C charge/discharge rates in the presence/absence of O2.
Figure 4: The typical self-discharge curves of LiTi2(PO4)3 in an aqueous electrolyte at pH 13.
Figure 5: Typical charge/discharge curves of the LiTi2(PO4)3/LiFePO4 aqueous lithium-ion battery.
Figure 6: Cycling life test of the LiTi2(PO4)3/LiFePO4 aqueous lithium-ion battery.

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Acknowledgements

We acknowledge the support of the National Natural Science Foundation of China (20633040, 20925312), the State Key Basic Research Program of PRC (2007CB209703), and Shanghai Science & Technology Committee (09XD1400300, 08DZ2270500).

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Authors and Affiliations

  1. Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Institute of New Energy, Fudan University, Shanghai, 200433, China

    Jia-Yan Luo, Wang-Jun Cui, Ping He & Yong-Yao Xia

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  1. Jia-Yan Luo
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  2. Wang-Jun Cui
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Contributions

J.L., W.C., P.H. and Y.X. conceived and designed the experiments, analysed and discussed results and commented on the manuscript. J.L. and W.C. performed the experiments and analysed the data. J.L. and Y.X. co-wrote the paper.

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Correspondence to Yong-Yao Xia.

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Luo, JY., Cui, WJ., He, P. et al. Raising the cycling stability of aqueous lithium-ion batteries by eliminating oxygen in the electrolyte. Nature Chem 2, 760–765 (2010). https://doi.org/10.1038/nchem.763

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