Synthesis of electrolytic manganese dioxide (EMD) and biomass waste-derived carbon for hybrid capacitors

Kethaki Wickramaarachchi

Renewable energy (RE) is expected to be the primary energy supplier in the future energy mix. This has created the necessity for low-cost, safe, and reliable energy storage to guarantee a continuous energy supply by the intermittent RE sources. Due to the inbuilt rich chemistry of manganese dioxide (MnO2) and the advantageous characteristics; of low cost, environmentally friendliness, and nontoxic, it can be adapted for a wide range of applications such as biosensors, humidity sensors, catalysts, and so on. Among the different forms of MnO2, electrolytic manganese dioxide (EMD) is well-demanded energy storage material. However, the limitations such as lower capacitance, irreversibility, and cyclability of EMD in comparison with other metal oxides such as cobalt and nickel oxides, have hindered its application in capacitor energy storage, which was one of the focuses of this thesis. Therefore, this Ph.D. research project aimed at synthesizing modified EMD materials as the positive electrode for hybrid capacitor applications. The modified EMD was coupled with the biomass-derived activated carbon (AC) which is synthesized as the negative electrode to fabricate hybrid capacitors. This Ph.D. research work has contributed to the existing knowledge through the following: 1) synthesizing pristine EMD using galvanostatic electrodeposition and studying its suitability for capacitor applications via experimental and theoretical analysis, 2) biopolymer alginate assisted EMD synthesis and optimization via experimental and computational modeling, 3) studying the effect of varying surfactants to improve the electrochemical characteristics of EMD, 4) synthesis of biomass waste-derived activated carbon and modeling their parameters for capacitance prediction. The results indicated the challenge and importance of the delicate tailoring of the EMD characteristics for capacitor application. Pristine EMD was synthesized under different electrodeposition experiment conditions by varying applied current density (100, 200, 300 A m-2) and deposition duration (4, 5, 6 h). The electrodeposition was carried out in a low acidic medium electrolytic bath where a lead (Pb) anode and stainless steel (SS) cathode were used. The EMD was deposited on the Pb anode via Mn2+ oxidation to form Mn4+ and its oxide MnO2. The physicochemical and electrochemical characterization of the obtained EMD powder concluded that the material deposited at 200 A m-2 for 5 hours, showing the spindle-like morphology was suitable over others for supercapacitor (SC) application. The pristine EMD at these experimental conditions delivered 98 F g-1 capacitance at 1 mA cm-2 applied current density tested in 2 M NaOH aqueous electrolyte and proved its potential development by modifying its characteristics. Therefore, the pristine EMD was modified by introducing the biopolymer alginic acid crosslinking to improve its electrochemical performance. The alginic acid was added to the electrolytic bath at varying concentrations; 0, 0.1, 0.25, 0.5, and 1 g l-1, to optimize the added bio-polymer amount to maximize the capacitance. At 0.5 g l-1, the pristine EMD morphology was rearranged to a cactus-shaped with flutes. The calculated specific capacitance of the modified EMD was ~5 times higher (487 F g-1) than the pristine EMD. The molecular dynamics simulation results determined the polymer-ion interactions in the electrolytic bath and provided evidence, showing that the alginic acid could act as a template for binding the Mn2+ ions in a relatively ordered manner for the growth of the EMD deposit. 0.42 of pyrolusite and 0.58 of ramsdellite fractions present in the modified material were quantitatively determined using the neutron powder diffraction (NPD) data. The slight increments of the lattice spacing observed in high-resolution transmission electron microscopy (HRTEM) images were well aligned with the NPD results of unit cell volume expansions of the EMD-polymer composite showing the polymer intercalation within the EMD structure influencing its characteristics. At 2 mA cm-2, the fabricated hybrid capacitor delivered 52 F g-1 specific capacitance, 14 Wh g-1 specific energy, 500 W g-1 specific power, and 94 % capacitance retention over 5000 cycles. The results highlighted the importance of the functional molecular structure of the biopolymer alginic acid to produce a binary composite of EMD-polymer as a capacitor material. Further, the pristine EMD was modified by electrodepositing the MnO2 using surfactant mediated electrolyte solutions. The electrochemical performance of the synthesized EMD in the presence of three novel cationic surfactants was compared with the pristine EMD and the EMD co-deposited with commonly used cetyltrimethylammonium ammonium bromide (C-AB) surfactant. The three surfactants with different molecular structures are Tetradecyltrimethylammonium bromide (T-AB), Didodecyldimethylammonium bromide (D-AB), Benzyldodecyldimethylammonium bromide (B-AB) used at varying concentrations (15, 30, 60 g l-1) in the electrolytic bath. Among the B-AB surfactant at 30 mg l-1, the EMD (EMD/B-AB30) showed the highest capacitance of 602 F g-1 tested at 1 mA cm-2 current density. The molecular dynamics simulation indicated that when the B-AB surfactant was attached to the Pb electrode via electrostatic, Van der Walls interactions, then the nucleation of MnO2 particles occurred surrounding the surfactant molecule. The unique molecular structure influenced the nucleation formation well-ordered, whereas, for pristine EMD, the nucleation was random. The hybrid capacitor comprises the best performed modified EMD (EMD/B-AB30), and biomass waste-derived AC exhibited 91 F g-1 specific capacitance, an outstanding energy density of 32.4 Wh kg-1 for a corresponding power density of 971 W kg-1. Valorization of the biomass waste, Mango seed husk (MS), and the Grape marc (GM) was carried out by converting the waste into AC for capacitor electrodes. The MS was carbonized, followed by chemical activation using KOH as the activating agent. Activation temperature was varied at 800, 900, 1000, and 1100 °C temperatures, among at 1100 °C highest surface area of 1943 m2 g-1, and the specific capacitance of 135 F g-1 was obtained for the MS-AC. The MS-AC experimental data were incorporated in four machine learning (ML) algorithms; linear regression (LR), decision tree (DT), support vector regression (SVR), and multi-layer perceptron (MLP) for capacitance prediction. Among, the MLP model showed the best correlation (R2 = 0.9868) between the experimental and predicted capacitance values and proved its potential application for computing the complex non-linear relationships between the input and output datasets. Further, the porous carbon materials were derived from GM using four synthesis routes by varying the parameters of activating agent (KOH and ZnCl2), dopant (Nitrogen), and carbonization (450, 600 °C) and activation (450, 800 °C) temperatures. Among the different GM-AC products, the GM carbon, doped with urea and activated by KOH (KACurea), exhibited better morphology, hierarchical pore structure, larger surface area (1356 m2 g-1), and the highest specific capacitance of 139 F g-1 in 2 M NaOH aqueous electrolyte. The miscellaneous collection of datasets based on AC experiments was used for specific capacitance and power prediction using the MLP ML model. Overall, this thesis showed that the EMD could be produced in bulk to be used for hybrid capacitor applications. Particularly, it provided insights about the specie interactions in the electrolyte solution that improved the material performance. This built the platform for further studies on altering the additive concentrations and combinations for developing high-performing EMD materials. This Ph.D. work also highlighted the opportunities to valorize the biomass waste to produce AC with desired characteristics of hierarchical pore structure, larger surface area, etc., to replace the conventional AC electrodes. Finally, the electrochemical performance of the hybrid capacitor fabricated using best performed EMD material (EMD/B-AB30) and biomass-waste derived AC (MS-AC 1100) surpassed the energy density values of the existing supercapacitors, proving its potential development in commercial applications.

Synthesis of electrolytic manganese dioxide (EMD) and biomass waste-derived carbon for hybrid capacitors

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