Drawbacks of Low Lattice Energy Ammonium Salts for Ion-Conducting Polymer Electrolyte Preparation: Structural, Morphological and Electrical Characteristics of CS:PEO:NH₄BF₄-Based Polymer Blend Electrolytes

• Main Authors: Mohamad A. Brza, Shujahadeen B. Aziz, Muaffaq M. Nofal, Salah R. Saeed, Shakhawan Al-Zangana, Wrya O. Karim, Sarkawt A. Hussen, Rebar T. Abdulwahid, Mohd F. Z. Kadir
• Format: Article
• Language: English
• Published: MDPI AG 2020-08-01
• Series: Polymers
• Subjects: polymer blend electrolyte; low lattice energy ammonium salts; degree of crystallinity; morphology study; impedance spectroscopy; dielectric properties
• Online Access: https://www.mdpi.com/2073-4360/12/9/1885

In the present work it was shown that low lattice energy ammonium salts are not favorable for polymer electrolyte preparation for electrochemical device applications. Polymer blend electrolytes based on chitosan:poly(ethylene oxide) (CS:PEO) incorporated with various amounts of low lattice energy NH₄BF₄ammonium salt have been prepared using the solution cast technique. Both structural and morphological studies were carried out to understand the phenomenon of ion association. Sharp peaks appeared in X-ray diffraction (XRD) spectra of the samples with high salt concentration. The degree of crystallinity increased from 8.52 to 65.84 as the salt concentration increased up to 40 wt.%. These are correlated to the leakage of the associated anions and cations of the salt to the surface of the polymer. The structural behaviors were further confirmed by morphological study. The morphological results revealed the large-sized protruded salts at high salt concentration. Based on lattice energy of salts, the phenomena of salt leakage were interpreted. Ammonium salts with lattice energy lower than 600 kJ/mol are not preferred for polymer electrolyte preparation due to the significant tendency of ion association among cations and anions. Electrical impedance spectroscopy was used to estimate the conductivity of the samples. It was found that the bulk resistance increased from 1.1 × 10⁴ ohm to 0.7 × 10⁵ ohm when the salt concentration raised from 20 wt.% to 40 wt.%, respectively; due to the association of cations and anions. The low value of direct current (DC) conductivity (7.93 × 10⁻⁷ S/cm) addressed the non-suitability of the electrolytes for electrochemical device applications. The calculated values of the capacitance over the interfaces of electrodes-electrolytes (C₂) were found to drop from 1.32 × 10⁻⁶ F to 3.13 × 10⁻⁷ F with increasing salt concentration. The large values of dielectric constant at low frequencies are correlated to the electrode polarization phenomena while their decrements with rising frequency are attributed to the lag of ion polarization in respect of the fast orientation of the applied alternating current (AC) field. The imaginary part of the electric modulus shows obvious peaks known as conduction relaxation peaks.