Impedance Spectroscopy Study of Solid Co(II/III) Redox Mediators Prepared with Poly(Ethylene Oxide), Succinonitrile, Cobalt Salts, and Lithium Perchlorate for Dye-Sensitized Solar Cells

مقال فى مجلة

2026

تم النشر فى: https://www.mdpi.com/2073-4360/18/1/142

Countries like Saudi Arabia receive abundant sunshine with exceptionally high solar irradiance. High temperatures in desert regions and the sunray angle dependence of solar modules are some of the key challenges of conventional solar cells. Dye-sensitized solar cells present a compelling alternative with the simple cell design and use of non-toxic materials without angle dependence, but their performance hinges on the solid redox mediators used for dye regeneration. These mediators must have an electrical conductivity (σ25°C) of more than 10−4 S cm−1 with an activation energy of less than 0.3 eV for device application. Our work focused on novel solid Co(II/III) redox mediators using cobalt complexes and LiClO4 in different matrices: pure PEO (an abbreviation for poly(ethylene oxide) with its redox mediator as M1), a [PEO–SN] blend (M2A and M2B with ethylene oxide to lithium ions molar ratio of 112.9 and 225.8, respectively), and pure SN (an abbreviation for succinonitrile with its redox mediator as M3). Impedance spectroscopy was the key technique, showing M1 and M2 behave like a mediator explainable with an (R1–C)-type circuit, while M3 is explainable with an (R1 − [R2‖C])-type circuit. M3 achieved the highest value of σ25°C with 2 × 10−3 S cm−1, while M1 had the lowest σ25°C, 3 × 10−5 S cm−1. M2 achieved an optimal balance with σ25°C of 4 × 10−4 S cm−1 (M2A) and 1.5 × 10−4 S cm−1 (M2B). M2 exhibited a remarkably low pseudo-activation energy of 0.042 eV and a Vogel–Tammann–Fulcher behavior ideal for consistent performance across temperatures. In contrast, M1 and M3 showed higher Arrhenius-type activation energies (>0.74 eV) in their solid states. These results correlated with those of the XRD, FT-IR spectroscopy, XPS, SEM, DSC, and TGA analyses. Ultimately, the [PEO–SN] blend emerges as a robust matrix, enabling the combination of high conductivity and low activation energy needed for a durable device in harsh environments.