Conjugated dicarboxylate anodes for Li-ion batteries

Abstract

Present Li-ion batteries for portable electronics are based on inorganic electrodes. For upcoming large-scale applications the notion of materials sustainability produced by materials made through eco-efficient processes, such as renewable organic electrodes, is crucial. We here report on two organic salts, Li2C8H4O4 (Li terephthalate) and Li2C6H4O4(Li trans–trans-muconate), with carboxylate groups conjugated within the molecular core, which are respectively capable of reacting with two and one extra Li per formula unit at potentials of 0.8 and 1.4 V, giving reversible capacities of 300 and 150 mA h g−1. The activity is maintained at 80 C with polyethyleneoxide-based electrolytes. A noteworthy advantage of the Li2C8H4O4 and Li2C6H4O4 negative electrodes is their enhanced thermal stability over carbon electrodes in 1 M LiPF6 ethylene carbonate–dimethyl carbonate electrolytes, which should result in safer Li-ion cells. Moreover, as bio-inspired materials, both compounds are the metabolites of aromatic hydrocarbon oxidation, and terephthalic acid is available in abundance from the recycling of polyethylene terephthalate.

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Figure 1: XRD of Li2C8H4O4 and Li2C6H4O4.
Figure 2: Potential–composition profile for Li2C6H4O4 and Li2C8H4O4, galvanostatically cycled at a rate of 1 Li+/10 h versus Li0.
Figure 3: Material evolution on cycling for Li2C8H4O4.
Figure 4: Material evolution on cycling for Li2C6H4O4.
Figure 5: Differential scanning calorimetry (DSC) measurements in the presence of electrolyte.

References

  1. 1

    The Economist Newspaper and the Economist Group. In search of the perfect battery, March 6th, (2008).

  2. 2

    Armand, M. & Tarascon, J. M. Building better batteries. Nature 451, 652–657 (2008).

    CAS  Article  Google Scholar 

  3. 3

    Kates, R. W. et al. Sustainability science. Science 292, 641–642 (2001).

    CAS  Article  Google Scholar 

  4. 4

    MacDiarmid, A. G., Yang, L. S., Huang, W. S. & Humphrey, B. D. Polyaniline: Electrochemistry and application to rechargeable batteries. Synth. Met. 18, 393–398 (1987).

    CAS  Article  Google Scholar 

  5. 5

    Novák, P., Müller, K., Santhanam, S.V. & Hass, O. Electrochemically active polymers for rechargeable batteries. Chem. Rev. 97, 207–281 (1997); and references cited therein.

  6. 6

    Qu, J. et al. Synthesis and charge/discharge properties of polyacetylenes carrying 2,2,6,6-tetramethyl-1-piperidinoxy radicals. Chem. Eur. J. 13, 7965–7973 (2007).

    CAS  Article  Google Scholar 

  7. 7

    Nishide, H. et al. Organic radical battery: nitroxide polymers as a cathode-active material. Electrochim. Acta 50, 827–831 (2004).

    CAS  Article  Google Scholar 

  8. 8

    Nakahara, K. et al. Rechargeable batteries with organic radical cathodes. Chem. Phys. Lett. 359, 351–354 (2002).

    CAS  Article  Google Scholar 

  9. 9

    Chen, H. et al. From biomass to the first example of a renewable LixC6O6 organic electrode for sustainable Li-ion batteries. ChemSusChem 1, 348–355 (2008).

    CAS  Article  Google Scholar 

  10. 10

    Armand, M., Michot, C. & Ravet, N. Redox and electrically conducting polyquinoid and related polymers for use as cathode materials in electrochemical generators, especially lithium batteries. PCT Int. Appl. 37 (1999).

  11. 11

    Le Gall, T., Reiman, H. R., Grossel, M. C. & Owen, J. R. Poly(2,5-dihydroxy-1,4-benzoquinone-3,6-methylene): A new organic polymer as positive electrode material for rechargeable lithium batteries. J. Power Sources 119–121, 316–320 (2003).

    Article  Google Scholar 

  12. 12

    Han, X., Chang, C., Yuan, L., Sun, T. & Sun, J. Aromatic carbonyl derivative polymers as high-performance Li-ion storage materials. Adv. Mater. 19, 1616–1621 (2007).

    CAS  Article  Google Scholar 

  13. 13

    Kaduk, J. A. Terephthalate salts: Salts of monopositive cations. Acta Crystallogr. 856, 474–485 (2000).

    Article  Google Scholar 

  14. 14

    Du Pasquier, A. et al. Differential scanning calorimetry study of the reactivity of carbon anodes in plastic Li-ion batteries. J. Electrochem. Soc. 145, 472–476 (1998).

    Article  Google Scholar 

  15. 15

    Wang, Y. & Dahn, J. R. Comparison of the reactions between LixSi or Li0.81C6 and non-aqueous solvents or electrolytes at elevated temperature. J. Electrochem. Soc. 153, A2188–A2191 (2006).

    CAS  Article  Google Scholar 

  16. 16

    Ohzuku, T., Ueda, A. & Yamamoto, N. Zero strain insertion material of Li[Li1/3Ti5/3]O4 for rechargeable Li cells. J. Electrochem. Soc. 142, 1431–1439 (1995).

    CAS  Article  Google Scholar 

  17. 17

    Peled, E. Lithium Stability and Film Formation in Organic and Inorganic Electrolytes for Lithium Battery Systems (Academic, 1983).

    Google Scholar 

  18. 18

    Aurbach, D. in Advances in Lithium-Ion Batteries (eds van Schalkwijk, W.A. & Scrosati, B.) (Kluwer–Academic/Plenum, 2002).

    Google Scholar 

  19. 19

    Herstedt, M. Towards Safer Lithium-Ion Batteries, Uppsala Dissertations from the Faculty of Science and Technology. Uppsala Univ., (2003).

  20. 20

    Rodríguez-Carvajal, J. Recent developments of the program FULLPROF. CPD Newslett. 26, 12 (2001); available at <http://www.iucr.org/iucr-top/news/index.html>. The program and documentation can be obtained from <http://www.ill.eu/sites/fullprof/index.html>.

  21. 21

    Thompson, P., Cox, D. E. & Hastings, J. B. Rietveld refinement of Debye–Scherrer synchrotron X-ray data from Al2O3 . J. Appl. Crystallogr. 20, 79–83 (1987).

    CAS  Article  Google Scholar 

  22. 22

    Neese, F. ORCA—an ab initio, density functional and semi-empirical program package, Univ. of Bonn, (2007).

  23. 23

    Bechgaard, K. & Parker, V. D. Mono-,di- and trications of hexamethoxytriphenylene. A novel anodic trimerization. J. Am. Chem. Soc. 94, 4749–4750 (1972).

    CAS  Article  Google Scholar 

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Acknowledgements

The authors thank M. Morcrette, F. Millange, and F. Wudl for discussions as well as N. Basir and M. Courty for their help in refining our X-ray data and running DSC experiments, respectively.

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Correspondence to J.-M. Tarascon.

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Armand, M., Grugeon, S., Vezin, H. et al. Conjugated dicarboxylate anodes for Li-ion batteries. Nature Mater 8, 120–125 (2009). https://doi.org/10.1038/nmat2372

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