SYNTHESIS, CHARACTERIZATION, AND ELECTROCHEMICAL PROPERTIES OF MESOPOROUS SPINEL LiMn2-xMxO4 (M = Mn, Fe, Co, Ni, AND Cu) THIN FILMS
By Irmak Karakaya Durukan
Advisor: Ömer Dağ
Bilkent University, Department of Chemistry
Date: 30.05.2024
Time: 11.00
Place: Chemistry Department Meeting Room (SB Building)
All are cordially invited to attend.
Abstract:
In this study, mesoporous LiMn2-xMxO4 (where M is Mn, Fe, Co, Ni, or Cu) thin films have been fabricated by employing molten-salt assisted self-assembly (MASA) method on fluorine doped tin oxide (FTO) surface. The electrochemical properties of the films are comprehensively investigated under acidic, alkaline, neutral, and non-aqueous solutions.
The manganese oxide-based electrodes undergo Mn(III) and Mn(VI) disproportionation reactions. Here, we have extensively investigated these disproportionation reactions by post-characterization techniques after electrochemical experiments using LiMn2-xMxO4 (M is Fe, Co, Ni, and Cu and x is 0, 0.1, 0.3, 0.4, and 0.67) and Mn3O4 electrodes. The LiMn2O4 thin films are found to be more stable in OER compared to Mn3O4. The electrochemical degradation rates are investigated using the LiMn2O4 electrodes, fabricated at various spin rates (from 2000 and 10000 rpm). The film thicknesses are between 150 and 500 nm. The LiMn2O4 electrode at 5000 rpm is more resistant to physical degradation during electrochemical tests. Charge capacity values of the thin films are determined by electrochemical experiments in LiNO3 electrolyte. The LiMn2O4 film, fabricated at 5000 rpm spin rate and annealed at 300 oC, is found to be a more robust and efficient electrode with a 60 mV/dec Tafel slope and 812 mV overpotential at 10 mA/cm2 current density The same fabrication parameters are used for the other mesoporous LiMn2-xMxO4 thin films.
The LiMn2-xMxO4 thin films are used to collect their N2-adsorption-desorption isotherms. The isotherms display type IV hysteresis, characteristic of mesoporous materials. BET surface areas are estimated as 98, 99, 116, 112, and 75 m2/g for the LiMn2O4, LiMn1.7Fe0.3O4, LiMn1.7Co0.3O4, LiMn1.7Ni0.3O4 and LiMn1.7Cu0.3O4, films, respectively. Moreover, the LiMn2-xMxO4 electrodes (fabricated at 5000 rpm spin rate and 300 oC annealing temperature) are investigated for lithium de-intercalation/intercalation behavior in 1 M LiNO3 solution. Then, the same electrodes are used to collect 300 CVs, CAs, and CPs in 1 M KOH solution to evaluate electrochemical behaviors. The Mn(VI) disproportionation reaction on the LiMn2-xMxO4 electrodes is investigated by CV cycling experiments in 1 M KOH. The LiMn2O4, LiMn2-xFexO4, and LiMn2-xCuxO4 electrodes undergo fast degradation compared to LiMn2-xCoxO4 and LiMn2-xNixO4 through the dispersion of [MnO4]- and [FeO4]2- ions and dissolution of the CuO phase formed in the electrodes during OER. The LiMn1.7M0.3O4 thin films on FTO are used in OER electrocatalysis and the overpotential values at 10 mA/cm2 are evaluated as 645, 686, and 657 mV for the LiMn1.7Fe0.3O4, LiMn1.7Co0.3O4, LiMn1.7Ni0.3O4 electrodes, respectively. The same compositions are also coated on graphite substrates and their overpotential values are also evaluated as 629, 462, 440, and 532 mV at 10 mA/cm2 for the LiMn2O4, LiMn1.7Fe0.3O4, LiMn1.7Co0.3O4, LiMn1.7Ni0.3O4 electrodes, respectively. The LiMn1.7Co0.3O4 on graphite and LiMn1.7Ni0.3O4 on FTO electrodes are found to be the most robust and efficient electrodes at a 50 mA/cm2 current density.
References:
1. Karakaya, F. Karadas, B. Ulgut, and Ö. Dag, Adv. Mater. Technol., vol. 5, no. 8, pp. 1–12, 2020.
2. I. K. Durukan, I. Ulu, and Ö. Dag, J. Mater. Chem. A, vol. 12, no. 11, pp. 6359–6375, 2024