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Smart Polymeric Cathode Material with Intrinsic Overcharge Protection Based on a 2,5-Di-tert-butyl- 1,4-dimethoxybenzene Core Structure

Authors

  • Wei Weng,

    1. Chemical Sciences and Engineering, Division & Material Sciences Division, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, IL 60439, USA
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  • Zhengcheng Zhang,

    Corresponding author
    1. Chemical Sciences and Engineering, Division & Material Sciences Division, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, IL 60439, USA
    • Chemical Sciences and Engineering, Division & Material Sciences Division, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, IL 60439, USA.
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  • Ali Abouimrane,

    1. Chemical Sciences and Engineering, Division & Material Sciences Division, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, IL 60439, USA
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  • Paul C. Redfern,

    1. Chemical Sciences and Engineering, Division & Material Sciences Division, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, IL 60439, USA
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  • Larry A. Curtiss,

    1. Chemical Sciences and Engineering, Division & Material Sciences Division, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, IL 60439, USA
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  • Khalil Amine

    1. Chemical Sciences and Engineering, Division & Material Sciences Division, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, IL 60439, USA
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Abstract

Polymer-based electroactive materials have been studied and applied in energy storage systems as a valid replacement for transition metal oxides. As early as 1999, Hass et al. proposed an interesting concept on the possible incorporation of both charge storage and overcharge protection functionality into a single material. However, there are virtually no examples of polymeric materials that can not only store the charge, but also consume the overcharge current. Herein, a new material based on a cross-linked polymer (I) with 2,5-di-tert-butyl-1,4-dimethoxybenzene as the core structure is reported. The cyclic voltammogram of the synthesized polymer shows a single oxidation/reduction peak at 3.9–4.0 V. At 1C rate (56 mA/g), polymer I shows stable cycling up to 200 cycles with <10% capacity loss. The redox shuttle mechanism remarkably can be activated when cell voltage is elevated to 4.3 V and the overcharge plateau at 4.2 V (2nd plateau) is persistent for more than 100 hours. The overcharge protection was due to the release of a chemical redox shuttle species in the electrolyte during the initial charging process. Both DFT calculations and NMR analysis of the aromatic signals in the 1H-NMR spectrum of electrolytes from “overcharged” cells provide evidence for this hypothesis.

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