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

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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.

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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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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.

Corresponding author

Correspondence to T. Brousse.

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The authors declare no competing financial interests.

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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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