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A high-energy-density and long-life lithium-ion battery via reversible oxide–peroxide conversion

Abstract

Li–O2 batteries have received considerable attention owing to their high theoretical gravimetric energy densities. However, the sluggish kinetic barrier between gaseous O2 and solid products leads to severe polarized overpotenial. Besides, the gas-open cell architecture and cumbrous O2 storage accessories bring additional burdens on practical application. Here, by pre-embedding Li2O nanoparticles into an iridium–graphene catalytic host, we confine the O2-free reversible Li2O/Li2O2 interconversion within a sealed cell environment. After rationally controlling the depth of charge, the O2/superoxo-free charge capacity can be extended to 400 mAh g–1 (based on the entire cathodic loading mass), with only 0.12 V round-trip overpotential. Ultrastable rechargeability can be achieved for over 2,000 cycles with 99.5% coulombic efficiency. Moreover, matched with a silicon anode, the full-cell output gravimetric energy density can reach nearly 600 Wh kg–1 (based on the loading mass of both electrodes). This work shows that reversible oxide–peroxide conversion can be utilized for the development of high-energy-density sealed battery technologies.

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Fig. 1: Schematic representations of oxygen-based beyond-intercalation Li battery systems.
Fig. 2: Characteristics of nano-Li2O embedded Iridium–rGO matrix.
Fig. 3: Characterization of the Li2O–Ir–rGO electrode during electrochemical transformation.
Fig. 4: Proposed reaction mechanism of Li2O oxidation.
Fig. 5: Rational charge/discharge depth for reversible Li2O/Li2O2 conversion on Li2O–Ir–rGO cathode.
Fig. 6: Cycling performance of half-cell (Li metal anode) and full-cell (Si anode) systems assembled with the Li2O–Ir–rGO cathode.

Data availability

All data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

References

  1. 1.

    Bruce, P. G., Freunberger, S. A., Hardwick, L. J. & Tarascon, J.-M. Li–O2 and Li–S batteries with high energy storage. Nat. Mater. 11, 19–29 (2012).

    CAS  Google Scholar 

  2. 2.

    Schmuch, R. et al. Performance and cost of materials for lithium-based rechargeable automotive batteries. Nat. Energy 3, 267–278 (2018).

    CAS  Google Scholar 

  3. 3.

    Lu, J. et al. Aprotic and aqueous Li–O2 batteries. Chem. Rev. 114, 5611–5640 (2014).

    CAS  PubMed  Google Scholar 

  4. 4.

    Luntz, A. C. & McCloskey, B. D. Nonaqueous Li–air batteries: a status report. Chem. Rev. 114, 11721–11750 (2014).

    CAS  PubMed  Google Scholar 

  5. 5.

    Lu, Y. C. et al. Lithium–oxygen batteries: bridging mechanistic understanding and battery performance. Energy Environ. Sci. 6, 750–768 (2013).

    CAS  Google Scholar 

  6. 6.

    Lim, H.-D. et al. Reaction chemistry in rechargeable Li–O2 batteries. Chem. Soc. Rev. 46, 2873–2888 (2017).

    CAS  PubMed  Google Scholar 

  7. 7.

    Liu, T. et al. Cycling Li–O2 batteries via LiOH formation and decomposition. Science 350, 530–533 (2015).

    CAS  PubMed  Google Scholar 

  8. 8.

    Lu, J. et al. A lithium–oxygen battery based on lithium superoxide. Nature 529, 377–382 (2016).

    CAS  PubMed  Google Scholar 

  9. 9.

    Xia, C., Kwok, C. Y. & Nazar, L. F. A high-energy-density lithium–oxygen battery based on a reversible four-electron conversion to lithium oxide. Science 361, 777 (2018).

    CAS  PubMed  Google Scholar 

  10. 10.

    Li, Y. & Lu, J. Metal–air batteries: will they be future electrochemical energy storage of choice? ACS Energy Lett. 2, 1370–1377 (2017).

    CAS  Google Scholar 

  11. 11.

    Freunberger, S. A. True performance metrics in beyond-intercalation batteries. Nat. Energy 2, 17091 (2017).

    Google Scholar 

  12. 12.

    Zhu, Z. et al. Anion-redox nanolithia cathodes for Li-ion batteries. Nat. Energy 1, 16111 (2016).

    CAS  Google Scholar 

  13. 13.

    Okuoka, S.-i et al. A new sealed lithium-peroxide battery with a Co-doped Li2O cathode in a superconcentrated lithium bis(fluorosulfonyl)amide electrolyte. Sci. Rep. 4, 5684 (2014).

    CAS  PubMed  PubMed Central  Google Scholar 

  14. 14.

    Kobayashi, H. et al. Improved performance of Co-doped Li2O cathodes for lithium-peroxide batteries using LiCoO2 as a dopant source. J. Power Sources 306, 567–572 (2016).

    CAS  Google Scholar 

  15. 15.

    Kobayashi, H. et al. Cathode performance of Co-doped Li2O with specific capacity (400 mAh/g) enhanced by vinylene carbonate. J. Electrochem. Soc. 164, A750–A753 (2017).

    CAS  Google Scholar 

  16. 16.

    Mahne, N. et al. Singlet oxygen generation as a major cause for parasitic reactions during cycling of aprotic lithium–oxygen batteries. Nat. Energy 2, 17036 (2017).

    CAS  Google Scholar 

  17. 17.

    Freunberger, S. A. et al. Reactions in the rechargeable lithium–O2 battery with alkyl carbonate electrolytes. J. Am. Chem. Soc. 133, 8040–8047 (2011).

    CAS  PubMed  Google Scholar 

  18. 18.

    Wang, Y. et al. Mechanistic insights into catalyst-assisted nonaqueous oxygen evolution reaction in lithium–oxygen batteries. J. Phys. Chem. C. 120, 6459–6466 (2016).

    CAS  Google Scholar 

  19. 19.

    Wang, Y. & Lu, Y.-C., Isotopic labeling reveals active reaction interfaces for electrochemical oxidation of lithium peroxide. Angew. Chem. Int. Ed. 58, https://doi.org/10.1002/ange.201901350 (2019).

    Google Scholar 

  20. 20.

    Pi, Y. et al. Ultrathin laminar Ir superstructure as highly efficient oxygen evolution electrocatalyst in broad pH range. Nano Lett. 16, 4424–4430 (2016).

    CAS  PubMed  Google Scholar 

  21. 21.

    Girishkumar, G. et al. Lithium–air battery: promise and challenges. J. Phys. Chem. Lett. 1, 2193–2203 (2010).

    CAS  Google Scholar 

  22. 22.

    Johnson, L. et al. The role of LiO2 solubility in O2 reduction in aprotic solvents and its consequences for Li–O2 batteries. Nat. Chem. 7, 1091–1099 (2015).

    Google Scholar 

  23. 23.

    Qiao, Y. et al. From O2 to HO2: reducing by-products and overpotential in Li–O2 batteries by water addition. Angew. Chem. Int. Ed. 56, 4960–4964 (2017).

    CAS  Google Scholar 

  24. 24.

    Chen, Y. et al. Li–O2 battery with a dimethylformamide electrolyte. J. Am. Chem. Soc. 134, 7952–7957 (2012).

    CAS  PubMed  Google Scholar 

  25. 25.

    Laoire, C. O. et al. Influence of nonaqueous solvents on the electrochemistry of oxygen in the rechargeable lithium-air battery. J. Phys. Chem. C. 114, 9178–9186 (2010).

    CAS  Google Scholar 

  26. 26.

    Viswanathan, V. et al. Electrical conductivity in Li2O2 and its role in determining capacity limitations in non-aqueous Li–O2 batteries. J. Chem. Phys. 135, 214704–214710 (2011).

    CAS  PubMed  Google Scholar 

  27. 27.

    McCloskey, B. D. et al. Limitations in rechargeability of Li–O2 batteries and possible origins. J. Phys. Chem. Lett. 3, 3043–3047 (2012).

    CAS  PubMed  Google Scholar 

  28. 28.

    Yao, K. P. C. et al. Solid-state activation of Li2O2 oxidation kinetics and implications for Li–O2 batteries. Energy Environ. Sci. 8, 2417–2426 (2015).

    CAS  Google Scholar 

  29. 29.

    Ohzuku, T. & Ueda, A. Solid-state redox reactions of LiCoO2 (R3m) for 4 volt secondary lithium cells. J. Electrochem. Soc. 141, 2972–2977 (1994).

    CAS  Google Scholar 

  30. 30.

    Zhang, T. & Zhou, H. A reversible long-life lithium–air battery in ambient air. Nat. Commun 4, 1817 (2013).

    PubMed  Google Scholar 

  31. 31.

    Li, F. J. et al. Performance-improved Li–O2 battery with Ru nanoparticles supported on binder-free multi-walled carbon nanotube paper as cathode. Energy Environ. Sci. 7, 1648–1652 (2014).

    CAS  Google Scholar 

  32. 32.

    Suo, L. et al. Fluorine-donating electrolytes enable highly reversible 5-V-class Li metal batteries. Proc. Natl Acad. Sci. 115, 1156–1161 (2018).

    CAS  Google Scholar 

  33. 33.

    Asadi, M. et al. A lithium–oxygen battery with a long cycle life in an air-like atmosphere. Nature 555, 502 (2018).

    CAS  PubMed  Google Scholar 

  34. 34.

    Gao, X. et al. A rechargeable lithium–oxygen battery with dual mediators stabilizing the carbon cathode. Nat. Energy 2, 17118 (2017).

    CAS  Google Scholar 

  35. 35.

    Pi, Y. et al. General formation of monodisperse IrM (M = Ni, Co, Fe) bimetallic nanoclusters as bifunctional electrocatalysts for acidic overall water splitting. Adv. Funct. Mater. 27, 1700886 (2017).

    Google Scholar 

  36. 36.

    Zhang, L. et al. A coordinatively cross-linked polymeric network as a functional binder for high-performance silicon submicro-particle anodes in lithium-ion batteries. J. Mater. Chem. A 2, 19036–19045 (2014).

    CAS  Google Scholar 

  37. 37.

    Frens, G. Controlled nucleation for regulation of particle-size in monodisperse gold suspensions. Nat. Phys. Sci. 241, 20–22 (1973).

    CAS  Google Scholar 

  38. 38.

    Li, J. F. et al. Shell-isolated nanoparticle-enhanced Raman spectroscopy. Nature 464, 392–395 (2010).

    CAS  PubMed  Google Scholar 

  39. 39.

    Hy, S. et al. Direct in situ observation of Li2O evolution on li-rich high-capacity cathode material, Li[NixLi(1–2x)/3Mn(2–x)/3]O2 (0 ≤ x ≤0.5). J. Am. Chem. Soc. 136, 999–1007 (2014).

    CAS  PubMed  Google Scholar 

  40. 40.

    Qiao, Y. et al. Li–CO2 electrochemistry: a new strategy for CO2 fixation and energy storage. Joule 1, 359–370 (2017).

    CAS  Google Scholar 

  41. 41.

    Qiao, Y. et al. MOF-based separator in an Li–O2 battery: an effective strategy to restrain the shuttling of dual redox mediators. ACS Energy Lett. 3, 463–468 (2018).

    CAS  Google Scholar 

  42. 42.

    McCloskey, B. D. et al. Solvents’ critical role in nonaqueous lithium-oxygen battery electrochemistry. J. Phys. Chem. Lett. 2, 1161–1166 (2011).

    CAS  PubMed  Google Scholar 

  43. 43.

    Beyer, H. et al. Antimony doped tin oxide–synthesis, characterization and application as cathode material in Li–O2 cells: implications on the prospect of carbon-free cathodes for rechargeable lithium–air batteries. J. Electrochem. Soc. 164, A1026–A1036 (2017).

    CAS  Google Scholar 

  44. 44.

    Schwenke, K. U. et al. The influence of water and protons on Li2O2 crystal growth in aprotic Li–O2 cells. J. Electrochem. Soc. 162, A573–A584 (2015).

    CAS  Google Scholar 

  45. 45.

    Kwak, W.-J. et al. Synergistic integration of soluble catalysts with carbon-free electrodes for Li–O2 batteries. ACS Catal. 7, 8192–8199 (2017).

    CAS  Google Scholar 

  46. 46.

    Schafzahl, B. et al. Quantifying total superoxide, peroxide, and carbonaceous compounds in metal–O2 batteries and the solid electrolyte interphase. ACS Energy Lett. 3, 170–176 (2018).

    CAS  Google Scholar 

  47. 47.

    Eisenberg, G. Colorimetric determination of hydrogen peroxide. Ind. Eng. Chem. Anal. Ed. 15, 327–328 (1943).

    CAS  Google Scholar 

  48. 48.

    Satterfield, C. N. & Bonnell, A. H. Interferences in titanium sulfate method for hydrogen peroxide. Anal. Chem. 27, 1174–1175 (1955).

    CAS  Google Scholar 

  49. 49.

    Li, F. J. et al. The water catalysis at oxygen cathodes of lithium–oxygen cells. Nat. Common. 6, 8843 (2015).

    Google Scholar 

  50. 50.

    Aetukuri, N. B. et al. Solvating additives drive solution-mediated electrochemistry and enhance toroid growth in non-aqueous Li–O2 batteries. Nat. Chem. 7, 50–56 (2015).

    CAS  PubMed  Google Scholar 

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Acknowledgements

This work was partially supported by the National Basic Research Programme of China (grant no. 2016YFB0100203) and NSF of China (grant no. 21633003, U1801251). Financial support from the Advanced Low Carbon Technology Research and Development Programme, specially promoting research for innovative next-generation batteries (SPRING), from the Japan Science and Technology Agency is acknowledged. H.D. acknowledges scholarships from the China Scholarship Council. We thank Y. Sun (NIMS, Japan), Z. Chang (AIST, Japan) and X. Mu (Nanjing University, China) for their help in DEMS characterization, schematic cartoon production and general discussion.

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Y.Q. and H.Z. contributed to the design of the research and performed the experimental data analysis. Y.Q. conducted the electrochemical and spectroscopic characterizations. K.J. performed the synthesis and assessment of the Ir–rGO cathodic substrate. H.D. performed the fabrication of both the Li2O-based cathode plate and related full-cell systems. All authors co-wrote the manuscript. H.Z. supervised the work. All authors discussed the results and commented on the manuscript.

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Correspondence to Haoshen Zhou.

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Supplementary Discussion, Supplementary Figs. 1–25, Supplementary Tables 1–3 and Supplementary References.

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Qiao, Y., Jiang, K., Deng, H. et al. A high-energy-density and long-life lithium-ion battery via reversible oxide–peroxide conversion. Nat Catal 2, 1035–1044 (2019). https://doi.org/10.1038/s41929-019-0362-z

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