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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The Economist Newspaper and the Economist Group. In search of the perfect battery, March 6th, (2008).
Armand, M. & Tarascon, J. M. Building better batteries. Nature 451, 652–657 (2008).
Kates, R. W. et al. Sustainability science. Science 292, 641–642 (2001).
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).
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.
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).
Nishide, H. et al. Organic radical battery: nitroxide polymers as a cathode-active material. Electrochim. Acta 50, 827–831 (2004).
Nakahara, K. et al. Rechargeable batteries with organic radical cathodes. Chem. Phys. Lett. 359, 351–354 (2002).
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).
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).
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).
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).
Kaduk, J. A. Terephthalate salts: Salts of monopositive cations. Acta Crystallogr. 856, 474–485 (2000).
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).
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).
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).
Peled, E. Lithium Stability and Film Formation in Organic and Inorganic Electrolytes for Lithium Battery Systems (Academic, 1983).
Aurbach, D. in Advances in Lithium-Ion Batteries (eds van Schalkwijk, W.A. & Scrosati, B.) (Kluwer–Academic/Plenum, 2002).
Herstedt, M. Towards Safer Lithium-Ion Batteries, Uppsala Dissertations from the Faculty of Science and Technology. Uppsala Univ., (2003).
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>.
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).
Neese, F. ORCA—an ab initio, density functional and semi-empirical program package, Univ. of Bonn, (2007).
Bechgaard, K. & Parker, V. D. Mono-,di- and trications of hexamethoxytriphenylene. A novel anodic trimerization. J. Am. Chem. Soc. 94, 4749–4750 (1972).
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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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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