Effect of Meso- and Micro-Porosity in Carbon Electrodes on Atomic Layer Deposition of Pseudocapacitive V2O5 for High Performance Supercapacitors
Commercially available activated carbon powders with varying microporous and mesoporous surface areas were characterized before and after ALD of V2O5 using nitrogen adsorption, FTIR, mass uptake, SEM and TEM analysis. An acid treatment of the activated carbon before ALD aided in V2O5 deposition. For the ALD process, we used vanadium tri-isopropoxide and water to grow thin films of amorphous V2O5 on the activated carbon electrodes. The V2O5 ALD on the high surface-area microporous carbon with pore diameters less than 11 Å decreased the net microporous surface area, thereby decreasing the available area for charge storage in the electrochemical double layer and the capacitance of the supercapacitor. The mesoporous carbon with slightly less starting surface area, however, showed increased charge storage capacity, consistent with more conformal coatings in the larger mesopores.
For the mesoporous electrodes, we used cyclic voltammetry, galvanostatic charging/discharging, and electrochemical impedance spectroscopy (EIS) to evaluate detailed changes in supercapacitor performance as a function of pseudocapacitive V2O5 ALD coating thickness. 1.5 nm thick films of V2O5 deposited on mesoporous carbon increased the capacitance by 46%. The V2O5 exhibited a maximum pseudocapacitance of 540 F/g(V2O5) from a 0.5 nm thick V2O5 film. Electrodes with up to 4.5 nm thick V2O5 films maintained high capacitive current (91-93% of total current), similar to uncoated electrodes (89%), and minimal diffusion limited current. Electrodes coated with 33 nm of V2O5 reported no net change in capacitance compared to uncoated electrodes due to decreased surface area (70% decrease) and reduced capacitive current (67% of total current). EIS analysis reported low equivalent series resistance for all of the electrodes, and similar capacitance and diffusion trends as seen with cyclic voltammetry. Electrodes coated with 4.5 nm of V2O5 maintained 89% capacitance after 10,000 charge/discharge cycles, compared to 88% for the uncoated electrodes.
This work demonstrates the basic challenges for ALD on highly porous electrodes, and points to further analysis of the V2O5 ALD process that could further improve supercapacitor performance.
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