Competition Between the Plasticizer and Polymer on Associating with Li + Ions in Polyacrylonitrile‐Based Electrolytes

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Abstract
The Raman and infrared spectra of the systems of plasticizer/ and plasticizer/polyacrylonitrile (PAN)/ have been recorded, where the plasticizer includes dimethylformamide (DMF) and propylene carbonate (PC). By comparing the spectra, it is found that the association of ion is more competitive with DMF than with PC in the liquid or gel electrolytes. Moreover, the addition of PAN into DMF/ solution has less influence on the ‐solvent association than into PC/ solution. Although a strong interaction has been observed between ions and PAN in PC//PAN electrolytes, no similar interaction is observed between ion and PAN in DMF/PAN/ system. However, after the plasticizer is removed from the gel electrolytes, apparent interaction is observed between ion and PAN. These phenomena lead to a conclusion that there is a competition between the plasticizer and the polymer for association with the ions in the PAN‐based electrolytes. In addition, it is found that the multiple ion aggregates are formed without the appearance of the usual “solvent‐shared ion aggregates” in the plasticizer‐free electrolyte, which suggests that the ions may move both in the gel state and with the segmental chain of PAN while the anion migrates mainly in the gel state in a practical PAN‐based electrolyte.

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