High-power positive electrode based on synergistic effect of N- and WO3 -decorated carbon felt for vanadium redox flow batteries

Although Vanadium Redox Flow Batteries (VRFB) are suitable for grid-scale applications, their power-related cost must be reduced in order to boost the use of this technology in the market, allowing their widespread commercialization. One effective way to make the VRFB a competitive and viable solution could be through new strategies for improving the electrocatalytic activity of the electrodes with enhanced electrolyte/electrode interface characteristics. Herein, we report the synergistic effect demonstrated by N- and WO3- decorated carbon-based positive electrode, named HTNW electrode, which demonstrates the feasibility of achieving: i) enhanced electrocatalytic activity, achieving large current density and high reversibility towards VO2+/VO2+ couple (promotion of oxygen and electron transfer processes), ii) decrement of the electron-transfer resistance from 76.18¿O to 13.00¿O for the pristine electrode and HTNW electrodes, respectively; iii) 51% of the electrolyte utilization ratio at high rates (i.e. 200¿mA¿cm-2) with 70% of energy efficiency; iv) increment of more than 50% of the power–peak in comparison with pristine electrode.Peer ReviewedPostprint (author's final draft

Adaptation of Cu(In, Ga)Se2 photovoltaics for full unbiased photocharge of integrated solar vanadium redox flow batteries

The integration of photovoltaics and vanadium redox flow batteries (VRFB) is a promising alternative for the direct conversion and storage of solar energy in a single device, considering their inherent higher energy density versus other redox pairs. However, this integration is not seamless unless the photovoltaic system is customized to the voltage needs of the battery, which unlike artificial photosynthesis, continuously increase with the state-of-charge. We have developed integrated solar VRFB with adapted low-cost Cu(In, Ga)Se2 modules of 3 and 4 series-connected cells (solar efficiency of mini-solar module 8.1%), and considering the voltage requirements (1.3-1.6V), we have evaluated the influence of the photovoltaic operation region on the final efficiency of the solar VRFB. Full unbiased photocharge under 1 Sun illumination has been achieved reaching high energy (77%), solar-to-charge (7.5%) and overall round trip energy conversion efficiencies (5.0%) excelling the values reported in literature for other solar VRFB, thus demonstrating the feasibility and intrinsic potential of adapting low-cost commercial photovoltaics to such energy storage systems.Peer ReviewedPostprint (author's final draft

Role of tungsten doping on the surface states in BiVO4 photoanodes for water oxidation: tuning the electron trapping process

The nanostructured BiVO4 photoanodes were prepared by electrospinning and were further characterized by XRD, SEM, and XPS, confirming the bulk and surface modification of the electrodes attained by W addition. The role of surface states (SS) during water oxidation for the as-prepared photoanodes was investigated by using electrochemical, photoelectrochemical, and impedance spectroscopy measurements. An optimum 2% doping is observed in voltammetric measurements with the highest photocurrent density at 1.23 VRHE under back side illumination. It has been found that a high PEC performance requires an optimum ratio of density of surface states (NSS) with respect to the charge donor density (Nd), to give both good conductivity and enough surface reactive sites. The optimum doping (2%) shows the highest Nd and SS concentration, which leads to the high film conductivity and reactive sites. The reason for SS acting as reaction sites (i-SS) is suggested to be the reversible redox process of V5+/V4+ in semiconductor bulk to form water oxidation intermediates through the electron trapping process. Otherwise, the irreversible surface reductive reaction of VO2+ to VO2+ though the electron trapping process raises the surface recombination. W doping does have an effect on the surface properties of the BiVO4 electrode. It can tune the electron trapping process to obtain a high concentration of i-SS and less surface recombination. This work gives a further understanding for the enhancement of PEC performance caused by W doping in the field of charge transfer at the semiconductor/electrolyte interface.Peer ReviewedPostprint (author's final draft

High-power positive electrode based on synergistic effect of N- and WO3 -decorated carbon felt for vanadium redox flow batteries

Although Vanadium Redox Flow Batteries (VRFB) are suitable for grid-scale applications, their power-related cost must be reduced in order to boost the use of this technology in the market, allowing their widespread commercialization. One effective way to make the VRFB a competitive and viable solution could be through new strategies for improving the electrocatalytic activity of the electrodes with enhanced electrolyte/electrode interface characteristics. Herein, we report the synergistic effect demonstrated by N- and WO3- decorated carbon-based positive electrode, named HTNW electrode, which demonstrates the feasibility of achieving: i) enhanced electrocatalytic activity, achieving large current density and high reversibility towards VO2+/VO2+ couple (promotion of oxygen and electron transfer processes), ii) decrement of the electron-transfer resistance from 76.18¿O to 13.00¿O for the pristine electrode and HTNW electrodes, respectively; iii) 51% of the electrolyte utilization ratio at high rates (i.e. 200¿mA¿cm-2) with 70% of energy efficiency; iv) increment of more than 50% of the power–peak in comparison with pristine electrode.Peer Reviewe

Adaptation of Cu(In, Ga)Se2 photovoltaics for full unbiased photocharge of integrated solar vanadium redox flow batteries

The integration of photovoltaics and vanadium redox flow batteries (VRFB) is a promising alternative for the direct conversion and storage of solar energy in a single device, considering their inherent higher energy density versus other redox pairs. However, this integration is not seamless unless the photovoltaic system is customized to the voltage needs of the battery, which unlike artificial photosynthesis, continuously increase with the state-of-charge. We have developed integrated solar VRFB with adapted low-cost Cu(In, Ga)Se2 modules of 3 and 4 series-connected cells (solar efficiency of mini-solar module 8.1%), and considering the voltage requirements (1.3-1.6V), we have evaluated the influence of the photovoltaic operation region on the final efficiency of the solar VRFB. Full unbiased photocharge under 1 Sun illumination has been achieved reaching high energy (77%), solar-to-charge (7.5%) and overall round trip energy conversion efficiencies (5.0%) excelling the values reported in literature for other solar VRFB, thus demonstrating the feasibility and intrinsic potential of adapting low-cost commercial photovoltaics to such energy storage systems.Peer Reviewe

Role of tungsten doping on the surface states in BiVO4 photoanodes for water oxidation: tuning the electron trapping process

The nanostructured BiVO4 photoanodes were prepared by electrospinning and were further characterized by XRD, SEM, and XPS, confirming the bulk and surface modification of the electrodes attained by W addition. The role of surface states (SS) during water oxidation for the as-prepared photoanodes was investigated by using electrochemical, photoelectrochemical, and impedance spectroscopy measurements. An optimum 2% doping is observed in voltammetric measurements with the highest photocurrent density at 1.23 VRHE under back side illumination. It has been found that a high PEC performance requires an optimum ratio of density of surface states (NSS) with respect to the charge donor density (Nd), to give both good conductivity and enough surface reactive sites. The optimum doping (2%) shows the highest Nd and SS concentration, which leads to the high film conductivity and reactive sites. The reason for SS acting as reaction sites (i-SS) is suggested to be the reversible redox process of V5+/V4+ in semiconductor bulk to form water oxidation intermediates through the electron trapping process. Otherwise, the irreversible surface reductive reaction of VO2+ to VO2+ though the electron trapping process raises the surface recombination. W doping does have an effect on the surface properties of the BiVO4 electrode. It can tune the electron trapping process to obtain a high concentration of i-SS and less surface recombination. This work gives a further understanding for the enhancement of PEC performance caused by W doping in the field of charge transfer at the semiconductor/electrolyte interface.Peer Reviewe

Pd2Sn [010] nanorods as a highly active and stable ethanol oxidation catalyst

The development of highly active, low cost and stable electrocatalysts for direct alcohol fuel cells remains a critical challenge. While Pd2Sn has been reported as an excellent catalyst for the ethanol oxidation reaction (EOR), here we present DFT analysis results showing the (100) and (001) facets of orthorhombic Pd2Sn to be more favourable for the EOR than (010). Accordingly, using tri-n-octylphosphine, oleylamine (OLA) and methylamine hydrochloride as size and shape directing agents, we produced colloidal Pd2Sn nanorods (NRs) grown in the [010] direction. Such Pd2Sn NRs, supported on graphitic carbon, showed excellent performance and stability as an anode electrocatalyst for the EOR in alkaline media, exhibiting 3 times and 10 times higher EOR current densities than that of Pd2Sn and Pd nanospheres, respectively. We associate this improved performance with the favourable faceting of the NRs.Peer ReviewedPostprint (published version

Pd2Sn [010] nanorods as a highly active and stable ethanol oxidation catalyst

The development of highly active, low cost and stable electrocatalysts for direct alcohol fuel cells remains a critical challenge. While Pd2Sn has been reported as an excellent catalyst for the ethanol oxidation reaction (EOR), here we present DFT analysis results showing the (100) and (001) facets of orthorhombic Pd2Sn to be more favourable for the EOR than (010). Accordingly, using tri-n-octylphosphine, oleylamine (OLA) and methylamine hydrochloride as size and shape directing agents, we produced colloidal Pd2Sn nanorods (NRs) grown in the [010] direction. Such Pd2Sn NRs, supported on graphitic carbon, showed excellent performance and stability as an anode electrocatalyst for the EOR in alkaline media, exhibiting 3 times and 10 times higher EOR current densities than that of Pd2Sn and Pd nanospheres, respectively. We associate this improved performance with the favourable faceting of the NRs.Peer Reviewe

Solar vanadium redox-flow battery powered by thin-film silicon photovoltaics for efficient photoelectrochemical energy storage

Solar-powered vanadium redox-flow batteries (VRFB) have emerged as an attractive method for large-scale and efficient energy storage and conversion. However, due to the stringent charging voltage requirements of vanadium-based systems (1.4–1.7 V), common photobatteries, applying standard photovoltaics with nonoptimized photovoltages, cannot be completely charged bias-free, i.e. by only using bias-free solar energy, or if they can be, only at unpractical low current densities of just a few mA cm-2. In response to this critical challenge, the present study aimed to design and test a compact device combining a high photovoltage silicon multijunction solar cell with an all-vanadium continuous-flow battery. In particular, we applied a monolithic triple junction solar cell, which can provide photovoltage of up to 2.2 V. Additionally, we have introduced the concept of increased illumination intensity for the solar VRFB. As a first demonstration, a complete bias-free solar charging at 25 mAcm-2 (300 mW cm-2 illumination) is reported. Moreover, we investigated the influence of the operation parameters of the redox-flow battery itself: the membrane type and the vanadium concentration in the electrolyte (i.e. storage capacity). The presented results provide evidence that the low-cost thin-film silicon based solar VRFB can be considered as an outstanding alternative for practical energy storage and conversion usage. A maximum bias-free solar conversion efficiency of 12.3% was achieved during charging, combined with promising and competitive energy efficiencies for the complete charge–discharge process that can guarantee an overall solar-to-electricity conversion efficiency of >10%.Peer Reviewe

Fe3O4@NiFexOy nanoparticles with enhanced electrocatalytic properties for oxygen evolution in carbonate electrolyte

The design and engineering of earth-abundant catalysts that are both cost-effective and highly active for water splitting are crucial challenges in a number of energy conversion and storage technologies. In this direction, herein we report the synthesis of Fe3O4@NiFexOy core shell nanoheterostructures and the characterization of their electrocatalytic performance toward the oxygen evolution reaction (OER). Such nanoparticles (NPs) were produced by a two-step synthesis procedure involving the colloidal synthesis of Fe3O4 nanocubes with a defective shell and the posterior diffusion of nickel cations within this defective shell. Fe3O4@NiFexOy NPs were subsequently spin-coated over ITO-covered glass and their electrocatalytic activity toward water oxidation in carbonate electrolyte was characterized. Fe3O4@NiFexOy catalysts reached current densities above 1 mA/cm(2) with a 410 mV overpotential and Tafel slopes of 48 mV/dec, which is among the best electrocatalytic performances reported in carbonate electrolyte.Postprint (published version