Unique Mechanisms of Ion Storage in Polyaniline Electrodes for Pseudocapacitive Energy Storage Devices Unraveled by EQCM-D Analysis
Turgeman M. Bergman G. Nimkar A. Gavriel B. Ballas E. Malchik F. Levi M.D. Sharon D. Shpigel N. Aurbach D.
19 October 2022American Chemical Society
ACS Applied Materials and Interfaces
2022#14Issue 4147066 - 47074 pp.
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.
aqueous batteries , EQCM-D , Na ion , polyaniline , redox polymers
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Department of Chemistry, BINA─BIU Center for Nanotechnology and Advanced Materials, Bar-Ilan University, Ramat-Gan, 5290002, Israel
Center for Physical and Chemical Methods of Research and Analysis, Al-Farabi Kazakh National University, Almaty, 050040, Kazakhstan
The Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem, 919040, Israel
Department of Chemistry
Center for Physical and Chemical Methods of Research and Analysis
The Institute of Chemistry
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