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

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.

References

  1. 1

    Li, W., Dahn, J. R. & Wainwright, D. Rechargeable lithium batteries with aqueous-electrolytes. Science 264, 1115–1118 (1994).

    CAS  Article  Google Scholar 

  2. 2

    Kohler, J., Makihara, H., Uegaito, H., Inoue, H. & Toki, M. LiV3O8: characterization as anode materials for an aqueous rechargeable Li-ion battery system. Electrochim. Acta. 46, 59–66 (2000).

    CAS  Article  Google Scholar 

  3. 3

    Wang, G. J., Fu, L. J., Zhao, N. H., Yang, L. C., Wu, Y. P. & Wu, H. Q. An aqueous rechargeable lithium battery with good cycling performance. Angew. Chem. Int. Ed. 46, 295–297 (2007).

    Article  Google Scholar 

  4. 4

    Wang, H. B., Huang, K. L., Zeng, Y. Q., Yang, S. & Chen, L. Q. Electrochemical properties of TiP2O7 and LiTi2(PO4)3 as anode materials for lithium ion battery with aqueous solution electrolyte. Electrochim. Acta. 52, 3280–3286 (2007).

    CAS  Article  Google Scholar 

  5. 5

    Luo, J. Y. & Xia, Y. Y. Aqueous lithium-ion battery LiTi2(PO4)3/LiMn2O4 with high power and energy densities as well as superior cycling stability. Adv. Funct. Mater. 17, 3877–3884 (2007).

    CAS  Article  Google Scholar 

  6. 6

    Huang, H., Yin, S. C. & Nazar, L. F. Approaching theoretical capacity of LiFePO4 at room temperature at high rates. Electrochem. Solid State Lett. 4, A170–A172 (2001).

    CAS  Article  Google Scholar 

  7. 7

    Li, W., McKinnon, W. R. & Dahn, J. R. Lithium intercalation from aqueous-solution. J. Electrochem. Soc. 141, 2310–2316 (1994).

    CAS  Article  Google Scholar 

  8. 8

    Li, W. & Dahn, J. R. Lithium-ion cells with aqueous electrolytes. J. Electrochem. Soc. 142, 1472–1746 (1995).

    Google Scholar 

  9. 9

    Zhang, M. J. & Dahn, J. R. Electrochemical lithium intercalation in VO2(B) in aqueous electrolyte. J. Electrochem. Soc. 143, 2730–2734 (1996).

    CAS  Article  Google Scholar 

  10. 10

    Dahn, J. R., Von Sacken, U., Juzkow, M. W. & Al Janaby, H. Rechargeable LiNiO2 carbon cells. J. Electrochem. Soc. 138, 2207–2211 (1991).

    CAS  Article  Google Scholar 

  11. 11

    McKinnon, W. R. & Haering, R. R. in Mordern Aspects of Electrochemistry (eds White, R. E., Bockris, J. O'M. & Conway, B. E.) No. 15 (Plenum Press, 1983).

    Google Scholar 

  12. 12

    Choi, J., Alvarez, E., Arunkumar, T. & Manthiram, A. Proton insertion into oxide cathode during chemical delithiation. Electrochem. Solid State Lett. 9, A241–A244 (2006).

    CAS  Article  Google Scholar 

  13. 13

    Choi, J. & Manthiram, A. Chemical and structural instabilities of lithium ion battery cathode. J. Power Sources 159, 249–253 (2006).

    Article  Google Scholar 

  14. 14

    Wang, Y. G., Luo, J. Y., Wang, C. X. & Xia, Y. Y. Hybrid aqueous energy storage cells using activated carbon and lithium-ion intercalated compound II. Comparison of LiMn2O4, LiCo1/3Ni1/3Mn1/3O2, and LiCoO2 positive electrodes. J. Electrochem. Soc. 153, A1425–A1431 (2006).

    CAS  Article  Google Scholar 

  15. 15

    Yu, D. Y. W. et al. Impurities in LiFePO4 and their influence on material characteristics. J. Electrochem. Soc. 155, A526–A530 (2008).

    CAS  Article  Google Scholar 

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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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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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The authors declare no competing financial interests.

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Luo, J., Cui, W., 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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