Synthesis and Application of P(EDOT-co-Py)@MWCNT Hybrid as Cathode Electrode for Aqueous Aluminum-Ion Batteries

A hybrid material based on the copolymerization of EDOT (3,4-ethylenedioxythiophene) and Py (pyrrole), 1:1 monomer ratio, onto multi-walled carbon nanotubes (MWCNTs) was synthesized through a multistep functionalization approach. The resulting P(EDOT-co-Py)@MWCNT hybrid, poly(3,4-ethylenedioxythiophene-co-pyrrol)@MWCNT hybrid, was characterized by Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA). These characterizations confirmed the successive functionalization steps, the effective anchoring of the monomers, and the subsequent formation of the copolymer. Transmission electron microscopy (TEM) images revealed a homogeneous polymer coating along the nanotube surface, while preserving the structural integrity of the MWCNTs throughout the functionalization and polymerization processes. The P(EDOT-co-Py)@MWCNT hybrid was evaluated as an active electrode material for aluminum-ion storage in aqueous aluminum sulfate electrolyte. The system exhibited two distinct charge-storage mechanisms: at high current densities, proton surface adsorption dominated, whereas at lower rates, a faradaic contribution associated with polymer chain redox activity and the reversible extraction/insertion of Al³⁺ became prevalent. The hybrid electrode delivered high specific capacities, reaching 200.6, 106.3, and 44.3 mAh g⁻¹ at 0.10, 0.25, and 0.50 A g⁻¹, respectively. These values are comparable to—or even exceed—those reported for similar cathodic materials designed for Al³⁺ storage, highlighting P(EDOT-co-Py)@MWCNT hybrid as a highly promising cathode candidate for aqueous aluminum-ion energy-storage systems.