Unique Mechanisms of Ion Storage in Polyaniline Electrodes for Pseudocapacitive Energy Storage Devices Unraveled by EQCM-D Analysis

Meital Turgeman, Gil Bergman, Amey Nimkar, Bar Gavriel, Elad Ballas, Fyodor Malchik, Mikhael D. Levi, Daniel Sharon, Netanel Shpigel*, Doron Aurbach

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

3 Scopus citations


The optimal performance of organic electrodes for aqueous batteries requires their full compatibility with selected electrolyte solutions. Electrode materials having 1-3-dimensional structures of variable rigidity possess a confined space in their structure filled with water and electrolyte solutions. Depending on the rigidity and confined space geometry, insertion and extraction of ions into electrode structures are often coupled with incorporation/withdrawal of water molecules. Aside from the scientific interest in understanding the charging mechanism of such systems, co-insertion of solvent molecules affects strongly the charge storage capability of the electrodes for energy storage devices. We present herein in situ electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) investigations of polyaniline (PANI) electrodes operating in various aqueous Na+-containing electrolytes, namely, Na2SO4, NaClO4, NaBF4, and NaPF6. Careful analysis of the EQCM-D results provides a dynamic snapshot of the mixed anionic/protonic fluxes and the accompanying water molecules' insertion/extraction to/from the PANI electrodes. Based on our observations, it was found that the charging mechanism, as well as the capacity values, strictly depends on the electrolyte pH, the chaotropic/kosmotropic character of the anionic dopants, and the amount of the extracted water molecules. This study demonstrates the effectiveness of analysis by EQCM-D in selecting electrolytes for batteries comprising organic electrodes.

Original languageAmerican English
Pages (from-to)47066-47074
Number of pages9
JournalACS applied materials & interfaces
Issue number41
StatePublished - 19 Oct 2022

Bibliographical note

Publisher Copyright:
© 2022 American Chemical Society.


  • EQCM-D
  • Na ion
  • aqueous batteries
  • polyaniline
  • redox polymers


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