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Safe and recyclable lithium-ion capacitors using sacrificial organic lithium salt

Nature Materials volume 17, pages 167–173 (2018)Cite this article

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Abstract

Lithium-ion capacitors (LICs) shrewdly combine a lithium-ion battery negative electrode capable of reversibly intercalating lithium cations, namely graphite, together with an electrical double-layer positive electrode, namely activated carbon. However, the beauty of this concept is marred by the lack of a lithium-cation source in the device, thus requiring a specific preliminary charging step. The strategies devised thus far in an attempt to rectify this issue all present drawbacks. Our research uncovers a unique approach based on the use of a lithiated organic material, namely 3,4-dihydroxybenzonitrile dilithium salt. This compound can irreversibly provide lithium cations to the graphite electrode during an initial operando charging step without any negative effects with respect to further operation of the LIC. This method not only restores the low CO2 footprint of LICs, but also possesses far-reaching potential with respect to designing a wide range of greener hybrid devices based on other chemistries, comprising entirely recyclable components.

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Figure 1: Design of lithium-ion capacitors (LICs) using different strategies for the prelithiation of the graphite negative electrode (blue: Li+ cation, red/white: PF6− anion).
Figure 2: Electrochemical behaviour of 3,4-dihydroxybenzonitrile dilithium salt in 1 mol l−1 LiPF6 dissolved in EC:DMC (vol. ratio 1:1).
Figure 3: Scheme showing oxidation of Li2DHBN to DOBN.
Figure 4: First galvanostatic charge of the LIC (graphite electrode pre-doping).
Figure 5: Galvanostatic charge/discharge of an LIC with a sacrificial composite positive electrode based on Li2DHBN.
Figure 6: Cycle life of different LICs designed with a sacrificial composite positive electrode based on Li2DHBN and a SEI formation (prelithiation performed at C/10).
Figure 7: Ragone plots of the LIC in 1 mol l−1 LiPF6 in EC:DMC, and of the EDLCs based on the same activated carbon, either in ACN/TEABF4 1 mol l−1 or in EC–DMC/LiPF6 1 mol l−1.

Change history

  • 15 December 2017

    In the version of this Article originally published, the text under the arrow in Fig. 3 should have read '–2e−; –2 Li+' instead of '–2e−; +2 Li+'. This has been corrected in all versions of the Article.

References

  1. Gogotsi, Y. & Simon, P. Materials for electrochemical capacitors. Nat. Mater. 7, 845–854 (2008).

    Article  Google Scholar 

  2. Stankovich, S. et al. Graphene-based composite materials. Nature 442, 282–286 (2006).

    Article  CAS  Google Scholar 

  3. Amatucci, G. G., Badaway, F., Pasquier, A. D. & Zheng, T. An asymmetric hybrid nonaqueous energy storage cell. J. Electrochem. Soc. 148, A930–A939 (2001).

    Article  CAS  Google Scholar 

  4. Naoi, K., Naoi, W., Aoyagi, S., Miyamoto, J.-I. & Kamino, T. New generation “ganohybrid supercapacitor”. Acc. Chem. Res. 46, 1075–1083 (2013).

    Article  CAS  Google Scholar 

  5. Naoi, K., Ishimoto, S., Miyamoto, J.-I. & Naoi, W. Second generation “nanohybrid supercapacitor”: evolution of capacitive energy storage devices. Energy Environ. Sci. 5, 9363–9373 (2012).

    Article  CAS  Google Scholar 

  6. Brousse, T., Marchand, R., Taberna, P. & Simon, P. TiO2 (B)/activated carbon non-aqueous hybrid system for energy storage. J. Power Sources 158, 571–577 (2006).

    Article  CAS  Google Scholar 

  7. Aida, T., Yamada, K. & Morita, M. An advanced hybrid electrochemical capacitor that uses a wide potential range at the positive electrode. Electrochem. Solid State Lett. 9, A534–A536 (2006).

    Article  CAS  Google Scholar 

  8. Khomenko, V., Raymundo-Piñero, E. & Béguin, F. High-energy density graphite/AC capacitor in organic electrolyte. J. Power Sources 177, 643–651 (2008).

    Article  CAS  Google Scholar 

  9. Park, M.-S. et al. A novel lithium-doping approach for an advanced lithium ion capacitor. Adv. Energy Mater. 1, 1002–1006 (2011).

    Article  CAS  Google Scholar 

  10. Jiang, G. & Pickering, S. J. Recycling supercapacitors based on shredding and mild thermal treatment. Waste Manage. 48, 465–470 (2016).

    Article  CAS  Google Scholar 

  11. Aida, T., Murayama, I., Yamada, K. & Morita, M. Improvement in cycle performance of a high-voltage hybrid electrochemical capacitor. Electrochem. Solid State Lett. 10, A93–A96 (2007).

    Article  Google Scholar 

  12. Sivakkumar, S. R. & Pandolfo, A. G. Evaluation of lithium-ion capacitors assembled with prelithiated graphite anode and activated carbon cathode. Electrochim. Acta 65, 280–287 (2012).

    Article  CAS  Google Scholar 

  13. Decaux, C., Lota, G., Raymundo-Piñero, E., Frackowiak, E. & Béguin, F. Electrochemical performance of a hybrid lithium-ion capacitor with a graphite anode preloaded from lithium bis(trifluoromethane)sulfonimide-based electrolyte. Electrochim. Acta 86, 282–286 (2012).

    Article  CAS  Google Scholar 

  14. Park, M.-S. et al. Scalable integration of Li5FeO4 towards robust, high-performance lithium-ion hybrid capacitors. ChemSusChem 7, 3138–3144 (2014).

    Article  CAS  Google Scholar 

  15. Park, M.-S. et al. Li2RuO3 as an additive for high-energy lithium-ion capacitors. J. Phys. Chem. C 117, 11471–11478 (2013).

    Article  CAS  Google Scholar 

  16. Lim, Y-G. et al. Anti-fluorite Li6CoO4 as an alternative lithium source for lithium ion capacitors: an experimental and first principles study. J. Mater. Chem. A 3, 12377–12385 (2015).

    Article  CAS  Google Scholar 

  17. Jeżowski, P., Fic, K., Crosnier, O., Brousse, T. & Béguin, F. Use of sacrificial lithium nickel oxide for loading graphitic anode in Li-ion capacitors. Electrochim. Acta 206, 440–445 (2016).

    Article  Google Scholar 

  18. Jeżowski, P., Fic, K., Crosnier, O., Brousse, T. & Béguin, F. Lithium rhenium(VII) oxide as a novel material for graphite prelithiation in high performance lithium-ion capacitors. J. Mater. Chem. A 4, 12609–12615 (2016).

    Article  Google Scholar 

  19. Aurbach, D., Zinigrad, E., Cohen, Y. & Teller, H. A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions. Solid State Ion. 148, 405–416 (2002).

    Article  CAS  Google Scholar 

  20. Goodenough, J. B. & Kim, Y. Challenges for rechargeable Li batteries. Chem. Mater. 22, 587–603 (2010).

    Article  CAS  Google Scholar 

  21. Lu, D. et al. Failure mechanism for fast-charged lithium metal batteries with liquid electrolytes. Adv. Energy Mater. 5, 1400993 (2015).

    Article  Google Scholar 

  22. Poizot, P. & Dolhem, F. Clean energy new deal for a sustainable world: from non-CO2 generating energy sources to greener electrochemical storage devices. Energy Environ. Sci. 4, 2003–2019 (2011).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  24. Armand, M. et al. Conjugated dicarboxylate anodes for Li-ion batteries. Nat. Mater. 8, 120–125 (2009).

    Article  CAS  Google Scholar 

  25. Chen, H. et al. Lithium salt of tetrahydroxybenzoquinone: toward the development of a sustainable Li-ion battery. J. Am. Chem. Soc. 131, 8984–8988 (2009).

    Article  CAS  Google Scholar 

  26. Renault, S., Geng, J., Dolhem, F. & Poizot, P. Evaluation of polyketones with N-cyclic structure as electrode material for electrochemical energy storage: case of pyromellitic diimide dilithium salt. Chem. Commun. 47, 2414–2416 (2011).

    Article  CAS  Google Scholar 

  27. Barrès, A.-L. et al. High-potential reversible Li deintercalation in a substituted tetrahydroxy-p-benzoquinone dilithium salt: an experimental and theoretical study. Chem. Eur. J. 18, 8800–8812 (2012).

    Article  Google Scholar 

  28. Renault, S. et al. A green Li–organic battery working as a fuel cell in case of emergency. Energy Environ. Sci. 6, 2124–2133 (2013).

    Article  CAS  Google Scholar 

  29. Gottis, S., BarreIs, A.-L., Dolhem, F. & Poizot, P. Voltage gain in lithiated enolate-based organic cathode materials by isomeric effect. ACS Appl. Mater. Interfaces 6, 10870–10876 (2014).

    Article  CAS  Google Scholar 

  30. Zhao, Q. et al. Rechargeable lithium batteries with electrodes of small organic carbonyl salts and advanced electrolytes. Ind. Eng. Chem. Res. 55, 5795–5804 (2016).

    Article  CAS  Google Scholar 

  31. Shanmukaraj, D. et al. Sacrificial salts: compensating the initial charge irreversibility in lithium batteries. Electrochem. Commun. 12, 1344–1347 (2010).

    Article  CAS  Google Scholar 

  32. Liu, T. et al. Substituent effects on the redox potentials of dihydroxybenzenes: theoretical and experimental study. Tetrahedron 70, 9033–9040 (2014).

    Article  CAS  Google Scholar 

  33. Schroeder, M., Winter, M., Passerini, S. & Balducci, A. On the cycling stability of lithium-ion capacitors containing soft carbon as anodic material. J. Power Sources 238, 388–394 (2013).

    Article  CAS  Google Scholar 

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Acknowledgements

The authors would like to express their gratitude to the Foundation for Polish Science (FNP) for funding the ECOLCAP project within the WELCOME programme, co-financed by the European Regional Development Fund. They also wish to thank the French Ministère des Affaires Etrangères and the Polish Ministerstwo Nauki i Szkolnictwa Wyższego (Polonium project # 31438NH). Kuraray, Solvay, Superior Graphite and Imerys are acknowledged for kindly providing the activated carbon, PVDF binder, graphite and Super C65 carbon black, respectively. The authors would like also to thank M. Olivard for preliminary experiments and Y. B. Moreau for helpful discussions about the manuscript.

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Authors and Affiliations

  1. Poznan University of Technology, Institute of Chemistry and Technical Electrochemistry, ul. Berdychowo 4, 60-965 Poznan, Poland

    P. Jeżowski & F. Béguin

  2. Institut des Matériaux Jean Rouxel, CNRS UMR 6502—Université de Nantes, 2 rue de la Houssinière BP32229, 44322 Nantes Cedex 3, France

    O. Crosnier, E. Deunf, P. Poizot & T. Brousse

  3. Réseau sur le Stockage Électrochimique de l’Énergie, FR CNRS 3459, 80039 Amiens Cedex, France

    O. Crosnier & T. Brousse

  4. Institut Universitaire de France (IUF), 1 rue Descartes, 75231 Paris Cedex 05, France

    P. Poizot

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  1. P. Jeżowski
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  2. O. Crosnier
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  6. T. Brousse
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Contributions

P.J., O.C., F.B. and T.B. conceived and designed the lithium-ion capacitor. P.P. selected the sacrificial lithiated organic salt. E.D., P.P. and P.J. were involved in its synthesis and related characterizations. P.J. performed the electrochemical experiments under F.B.’s guidance. P.P., T.B., F.B. and P.J. wrote the paper and commented on the results with the assistance of E.D. and O.C.

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Correspondence to T. Brousse.

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Jeżowski, P., Crosnier, O., Deunf, E. et al. Safe and recyclable lithium-ion capacitors using sacrificial organic lithium salt. Nat. Mater. 17, 167–173 (2018). https://doi.org/10.1038/nmat5029

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