Turbostratic Carbon Nano Onion Electrode for High Power Density Vanadium Redox Flow Battery
Authors: Fiorini Granieri Simone , Pagano Gerardo Maria , Cecchetti Marco , Radinger Hannes , Scheiba Frieder , Zago Matteo , Casalegno Andrea , Di Fonzo Fabio 
Published: February 2024

The redox flow battery (RFB) is one of the most promising technologies for stationary energy storage. It consists of a voltaic cell whose electrolytes are stored in tanks outside the system. Whilst the chemistries of the anodic and cathodic electrolytes define the energy density of a RFB system, its power density is determined primarily by its electrodes. These are typically porous carbon media on the surface of which the redox reactions occur. They are a critical component since they require a detailed engineering of electrocatalytically active surface area and mass transport. Still today, they remain the main cause of RFB low power density. In this work, we are showing a novel deposition method to improve the performance of commercially available carbon paper already used in RFB.
The gain is thanks to the deposition of turbostratic carbon nano-onion (TCNO) nanoparticles on the carbon fibers of the paper. This process is performed with a proprietary technology called NanoJeD: a CVD in supersonic flow, which promises easy industrial scalability and a fine tunability of the nanoparticle properties. Moreover, with this system is possible to deposit over any substrate.
NanoJeD consists in two chambers separated by a high aspect ratio slit. A precursor gas is injected through a porous plug from the top and a vacuum system is connected from the bottom. The slit allows the establishment of a high-pressure ratio between the two chambers and hence the formation of a supersonic jet. The precursor gas, a mixture of Argon (98.4%) and Acetylene (1.6%) flows between two electrodes where a radio frequency (RF) signal is fed (13.56 MHz). The RF ignites a non-thermal plasma in which the precursor molecules are ionized and dissociated into radicals, which polymerize forming hydrogenated carbon clusters and nanoparticles (NPs) of different sizes. Once formed, NPs are dragged through the slit by the gas stream and finally impact on the substrate. Therefore, it is possible to achieve a high throughput (500 mg h-1) and to deposit on a large area of 100 cm2 while precisely controlling the properties of the film. The resulting film has hundreds of squared meters per gram of surface area. For TCNO formation, the NP film is further annealed in vacuum at 1000°C for 2 hours. Using in situ transmission electron microscopy (TEM) and energy electron loss spectroscopy (EELS), we were able to visualize the progression of graphitization and changes in structural properties during annealing. The graphitization process starts in the outer layer and proceeds into the interior of the particle. The geometrical constrains of the NP (average diameter of 20nm) and shrinkage of the NP, allow the formation of curved, turbostratic, defective graphitic sheets. UV photoelectron spectroscopy (UPS) and Raman spectroscopy performed ex-situ allow the analysis of valence bands and structural defects. The high presence of defects and general disorder structure are accompanied with a remarkable increase in catalytic activity. Moreover, the annealing process leads to the sintering of the nanoparticles and the formation of an interface between the carbon fibre and the nanoparticles, as demonstrated by the increased thermal stability tested by. Both phenomena improve the adhesion between nanoparticles and with the surface, making the electrode suitable to be adopted in fluxed systems.
The TCNO deposited on a carbon paper was tested as electrode in a Vanadium RFB. The kinetic activity and electrochemical properties were tested via in-situ Raman and in a three-electrode cell set-up. The results reveal an increased kinetic activity with respect to the untreated paper. Using in situ Raman we were able to show differences in redox mechanism between TCNO and bare carbon paper. A chronoamperometry test was used to obtain the transfer coefficient from a Tafel plot. These studies allow the correlation of the catalytic activity with the defectiveness of the TCNO nanoparticle. Vanadium RFB full cell measurements of the TCNO electrode show a drastic increase in performance, reaching an energy efficiency of 70.8% and 86.2% at current densities of 600 mA cm-2 and 200 mA cm-2, respectively. The electrolyte utilisation for these current densities is 59% for the former and 80% for the latter. To investigate the chemical and mechanical stability a stability test was performed. Results showed a low degradation rate of 0.004% EE per cycle. Moreover, TCNO can be used for other electrochemical applications only by adjusting the deposition and annealing parameters.