Search Results (227)

The proton (H⁺) and vanadium ion (Vⁿ⁺) selectivity of proton-conductive membrane is one of the key components for vanadium redox flow batteries (VRFBs). In this work, a hydrophobic side chain was designed to accelerate proton conduction with high selectivity of H⁺ and Vⁿ⁺ for the VRFB membrane. The grafting of hydrophobic butyl side chains into the membrane (PBIOSO₃-But) induced the formation of a high microphase separation capacity to form large and connected ion conductive channels with low ion exchange capacity (IEC). As a result, the PBIOSO₃-But membrane with low IEC of 1.26 mmol g⁻¹ shows area resistance of 0.19 Ω cm² as well as vanadium permeability of 3.2 × 10⁻⁹ cm² s⁻¹, leading to a high H⁺/Vⁿ⁺ selectivity of 2.51 × 10¹⁰ mS s cm⁻³ (higher than Nafion 212, 4.62 × 10⁸ mS s cm⁻³). Notwithstanding its low ion-exchange capacity, this membrane demonstrates H⁺/Vⁿ⁺ selectivity surpassing that of recently reported microphase separation membranes. Compared to the Nafion 212 membrane (74.3% EE; 0.81% per cycle), the PBIOSO₃-But membrane exhibited superior VRFB performance, achieving an energy efficiency of 83.2% at 200 mA cm⁻² and a low retention rate of 0.22% per cycle. These values compare favorably with those of recently reported membranes. Full article

This study develops a lifecycle economic comparison framework for shared energy storage, in which multiple users share a common storage asset through capacity leasing. A multi-service revenue structure, including capacity leasing, spot-market arbitrage, auxiliary frequency regulation, peak shaving, and capacity compensation, is established for comparative evaluation. Case studies are conducted for lithium iron phosphate (LFP) and vanadium redox flow (VRF) batteries across six representative Chinese electricity markets and six standardized revenue-combination scenarios. The results show that, among the scenarios that more closely reflect current operating practices, P3 (capacity compensation + spot market + auxiliary frequency regulation) delivers the highest net present value (NPV). P6 combines all five revenue streams without explicitly modeling service-coupling dispatch constraints, and is therefore treated as a theoretical benchmark rather than an immediately deployable operating mode. Under this benchmark assumption, its calculated NPV is 21.1% and 41.7% higher than that of P3 for the two battery types, respectively. The study also shows that power-related services are more sensitive to rated power, while spot-market and peak-shaving revenues are more dependent on rated capacity. Full article

The increasing penetration of renewable energy sources (RES) introduces significant variability and instability in modern power systems, creating a growing need for advanced and coordinated energy storage solutions. However, a key unresolved challenge remains the integrated modeling and optimal sizing of hybrid energy storage systems (ESS) that combine technologies with different temporal characteristics under high RES penetration. This study addresses this challenge by developing a unified techno-economic and physical–mathematical framework for hybrid ESS integrating lithium-ion (Li-ion), vanadium redox flow batteries (VRFB), and hydrogen (H₂) technologies. Unlike conventional approaches that treat storage technologies independently or use simplified hybrid representations, the proposed framework jointly considers dynamic energy balance, degradation-aware lifecycle behavior, and multi-criteria cost optimization. The model was implemented using Python 3.10-based simulation tools and evaluated under renewable penetration scenarios of 30%, 50%, and 70%. The results indicate that increasing RES penetration leads to higher power fluctuations, reaching ±15–20% at 50% RES and ±20–25% at 70% RES. The optimized hybrid system achieves an overall efficiency of up to 92%, reduces total system cost to approximately 450 USD/kWh, and extends operational lifetime to 25 years, demonstrating a balanced techno-economic performance compared to standalone storage technologies. The proposed framework addresses this gap by coupling dynamic energy balance analysis with degradation-aware techno-economic optimization, enabling coordinated allocation of storage functions across short-, medium-, and long-duration timescales. In this way, the study not only evaluates hybrid storage performance, but also provides a practical decision-support framework for renewable-dominated power systems, particularly in the context of Kazakhstan’s energy transition. Full article

As power-electronic-interfaced renewable generation displaces synchronous machines, modern power systems face coupled day-ahead challenges: net-load variability demands peak shaving, while declining inertia necessitates explicit frequency-regulation scheduling. In sequential security-constrained unit commitment (SCUC) and Security-Constrained Economic Dispatch (SCED), the reserve procured in SCUC may lose deliverability after redispatch because the same storage bandwidth is reassigned to energy service. This paper proposes a two-stage day-ahead framework that addresses both challenges for low-inertia systems with high inverter-based resource (IBR) penetration. Stage I embeds Rate-of-Change of Frequency (RoCoF), frequency nadir, and quasi-steady-state (QSS) constraints in SCUC, with a piecewise-linear outer approximation for the non-convex nadir limit. Stage II strictly inherits the SCUC commitment and reserve reservation, and it applies bandwidth deduction to prevent peak-shaving redispatch from consuming committed frequency reserve. A technology-aware partition further assigns fast-response Lithium Iron Phosphate (LFP) batteries to sub-second frequency support and long-duration Vanadium Redox Flow Batteries (VRFBs) to energy shifting. Evaluated under the adopted reduced-order frequency-response framework and disturbance representation, tests on a modified IEEE 39-bus system under an extreme-wind scenario demonstrate that explicit frequency constraints eliminate all post-contingency violations, the inheritance mechanism closes a 23.85 MW reserve gap after redispatch, and heterogeneous storage partitioning preserves essentially the same disturbance sensitivity while increasing the peak-shaving ratio to 45.85%, lowering the day-ahead cost to CNY $10.483\times {10}^6$ and reducing the average system price to 209.33 CNY/MWh. Full article

In recent years, flow batteries have emerged as a crucial technological solution for large-scale energy storage, leveraging their unique power-capacity decoupling characteristics and long cycle life to demonstrate significant potential in applications such as renewable energy integration and grid frequency regulation. Based on differences in electrolyte systems, mainstream flow battery technologies are primarily categorized into three types: all-vanadium redox flow batteries (VRFBs), iron-chromium redox flow batteries (ICFBs), and zinc-based redox flow batteries (ZRFBs). However, each of these technologies faces critical challenges in practical commercialization: VRFBs are constrained by cost pressures due to fluctuations in vanadium resource prices and relatively low energy efficiency; ICFBs require urgent solutions to issues such as hydrogen evolution side reactions at the negative electrode and the sluggish kinetic responses of the Cr³⁺/Cr²⁺ redox couple; while ZRFBs grapple with safety concerns such as zinc dendrite growth and morphology instability. To overcome these technical bottlenecks, extensive innovative research has been conducted in key materials (electrodes, ion-exchange membranes, electrolytes). Against this backdrop, this paper systematically reviews recent advances in the modification and optimization of flow battery technologies and conducts an extended discussion on the emerging organic redox flow batteries in recent years. Full article

Ports located within dense urban environments face a major challenge in achieving deep decarbonization without compromising the reliability and safety of critical maritime operations. This study develops and validates a resilience-oriented control and sizing typology for Hybrid Renewable Energy Systems (HRESs), supporting the transition of a medium-sized Mediterranean port toward a Nearly Zero Energy Port (nZEP). The framework integrates five years of measured electrical demand at 15 min resolution to capture stochastic load variability, seasonal effects, and safety-critical peak events. Thirty-five HRES configurations are simulated using HOMER Pro, assessing photovoltaic and wind generation combined with alternative Energy Storage System (ESS) technologies under two grid-interface control strategies: Net Metering (NM) and non-NM curtailment-based operation. Conventional Lead–Acid batteries are compared with inherently safer Vanadium Redox Flow Batteries (VRFBs), while autonomy constraints of 24 h and 48 h are imposed to represent operational resilience. System performance is evaluated through a multi-criteria framework encompassing economic viability (Levelized Cost of Energy), environmental impact (Lifecycle Assessment-based carbon footprint), and operational reliability. Results indicate that NM-enabled HRES architectures significantly outperform non-NM configurations by exploiting the external grid as an active balancing layer. The optimal NM configuration achieves a Levelized Cost of Energy of 0.063 €/kWh under a 24 h autonomy constraint, while reducing operational carbon intensity to approximately 70 gCO₂,eq/kWh, corresponding to a reduction exceeding 90% relative to baseline grid-dependent operation. In contrast, non-NM systems require substantial storage and generation oversizing to maintain resilience, resulting in higher curtailment losses and Levelized Cost of Energy values of 0.12–0.15 €/kWh. Across both control regimes, VRFB-based systems consistently exhibit superior robustness and safety performance compared to Lead–Acid alternatives. The proposed typology provides a transferable framework for resilient and low-carbon port microgrid design under real-world operational constraints. Full article

This study aims to address the limitations of dense polyvinylidene fluoride (PVDF) membranes grafted with vinyl ethyl imidazole tetrafluoroborate, which exhibit low hydrophilicity and ionic conductivity in vanadium redox flow batteries (VRFBs). To improve these properties, water-soluble β-cyclodextrin was introduced as a porogen to fabricate asymmetric porous membranes. The porous structure was controlled by varying the porogen content (10–50 wt%), and the resulting membranes were characterized using FTIR, SEM, TGA, and electrochemical tests. This unique architecture led to a significant enhancement in ionic conductivity (to 71.69 mS/cm, from 6.73 mS/cm for the dense membranes), porosity (up to 40.24%), and water uptake (up to 31.8%), while maintaining robust mechanical strength (tensile strength 14.96 MPa) suitable for VRFB assembly and operation. In single-cell performance tests across a range of current densities, clear trends emerged: Coulombic efficiency (CE) decreased with higher porosity, whereas voltage efficiency (VE) followed the opposite trend. Consequently, the optimal energy efficiency (EE) was achieved with the intermediate porogen content, successfully balancing conductivity and selectivity. This work demonstrates a green and scalable approach to developing high-performance porous membranes for VRFB applications. Full article

A novel membrane was synthesized in this work by grafting 1-vinyl-3-ethylimidazolium tetrafluoroborate ([C₂VIm][BF₄]) onto a polyvinylidene fluoride (PVDF) backbone, followed by the introduction of a sulfonated graphene oxide (SGO) dispersion into the polymer solution. This composite was transformed into a composite proton-conducting membrane via a solution casting process and subsequently underwent protonation. Successful grafting was confirmed using analytical techniques including Fourier Transform Infrared Spectroscopy (FTIR), ¹H Nuclear Magnetic Resonance (NMR) and X-ray Photoelectron Spectroscopy (XPS). Scanning Electron Microscopy with Energy Dispersive X-ray Spectroscopy (SEM-EDS) analysis verified the homogeneous distribution of the SGO filler. Analysis reveals that incorporating SGO as a filler substantially augments the performance of anion exchange membranes. Key enhancements include a tensile strength increase to 37.97 MPa, water uptake of 10.34%, an ion exchange capacity of 1.68 mmol/g, and the through-plane proton conductivity of 15.47 mS/cm. While vanadium permeability rose marginally to 2.02 × 10⁻⁷ cm²/min, it remains drastically lower than that of Nafion 115. The composite proton-conducting membrane also displayed robust chemical stability. The membrane was finally integrated into a vanadium redox flow battery (VRFB) for performance evaluation. At a current density of 100 mA/cm², it exhibits a satisfactory coulombic efficiency (CE) of 97.84%, excellent capacity retention, and superior cycling stability. These results demonstrate that the PVDF-g-IL/SGO-based composite proton-conducting membrane is an ideal candidate material for vanadium flow battery applications. Full article

Vanadium redox flow batteries (VRFBs) experience performance losses driven by electrode ageing, yet the underlying mechanisms remain poorly resolved under operational conditions. This work presents a novel application of dynamic electrochemical impedance spectroscopy (DEIS) in both full-cell and three-electrode configurations to monitor kinetic and transport processes throughout complete charge–discharge cycles. Carbon felt electrodes subjected to thermal activation, chemical degradation, and electrochemical ageing were systematically examined to capture a broad range of ageing-induced modifications. Complementary electrochemical impedance spectroscopy (EIS) measurements at selected states of charge were performed to highlight the substantial differences between spectra recorded under load and at open-circuit conditions. The results reveal that the impedance response of the full cell is dominated by processes occurring at the negative electrode, and that ageing leads to increased charge-transfer resistance and enhanced state of charge-dependent variation. X-ray photoelectron spectroscopy (XPS) analysis confirms significant modifications in surface chemistry, including variations in the sp²/sp³ carbon distribution and the enrichment of oxygen-containing functional groups, which correlate with the observed electrochemical behavior. Overall, this study demonstrates—for the first time under realistic VRFB cycling conditions—that DEIS provides unique diagnostic capabilities, enabling mechanistic insights into electrode ageing that are inaccessible to conventional impedance approaches. Full article

The power allocation in Vanadium Redox Flow Battery (VRB) energy storage systems faces a conflict between long-term lifespan and real-time power coupling. Using a single-layer optimization method to directly address multiple objectives simultaneously may lead to conflicts among these objectives. Therefore, this paper presents a multi-objective two-layer optimization allocation strategy. Its core is hierarchical scheduling for long/short-term goals to optimize multi-attribute objectives precisely. A two-layer model comprising an initial allocation layer and an operational optimization layer is constructed to ensure the prioritization of long-term lifespan objectives based on a predefined hierarchical structure. The initial allocation layer focuses on the long-term objective of energy storage capacity lifespan, by prioritizing minimal capacity degradation. A differential evolution algorithm is then applied to perform preliminary allocation of the total power demand. The operational optimization layer aims to achieve optimal State of Charge (SOC) balance across all units and minimize power losses. An Adaptive Multi-Objective Harris Hawks Optimizer (ASAMOHHO) based on adaptive simulated annealing is established to find the Pareto optimal solution set, and ultimately determining the real-time power allocation plan for each unit. Comparative simulations with conventional methods were conducted, and the results demonstrate that the proposed strategy provides an efficient and practical solution for efficient VRB scheduling. Full article

Vanadium redox flow batteries, as a key technology for energy storage systems, have gained application in recent years. Investigating the thermal behavior and performance of these batteries is crucial. This study establishes a three-dimensional model of a vanadium redox flow battery featuring a serpentine flow channel design. By adjusting key battery parameters, changes in ion concentration and uniformity are examined. The model integrates electrochemical, fluid dynamics, and Physico-Chemical Kinetics phenomena. Electrolyte flow velocity and current density are critical parameters. Results indicate that increasing the electrolyte inlet flow velocity leads to convergence in the battery’s charge/discharge cell voltage, ${\mathrm{VO}}_2^{+}{/\mathrm{VO}}^{2+}$, ${\mathrm{V}}^{2+}{/\mathrm{V}}^{3+}$ and concentration distribution across the carbon felt and flow channels. Coincidently, the uniformity of vanadium ions across all oxidation states improves. Furthermore, the observed ion uniformity and battery cell voltage are shown to be significantly modulated by the system’s State of Charge, which sets the baseline electrochemical environment for flow rate effects. Full article

The EU’s green transition hinges on secure access to critical raw materials; vanadium is pivotal for microalloyed steels and emerging long-duration energy storage (VRFBs). Methods: We combine a market and technology review with PESTEL and Porter-5+2 analyses, complemented by a value-chain assessment and a SWOT-to-CAME strategy for the EU. Results: Vanadium supply is highly concentrated (VTM-derived, largely in CN/RU/ZA), prices are volatile, and >85% of demand remains tied to steel; yet VRFBs could shift demand shares by 2030 if costs—dominated by electrolyte—are mitigated. EU weaknesses include lack of primary mining and refining capacity; strengths include research leadership, regulatory frameworks and circularity potential (slag/catalyst recovery, electrolyte reuse). Conclusions: A resilient EU strategy should prioritize circular supply, selective upstream partnerships, battery-grade refining hubs, and targeted instruments (strategic stocks, offtake/price-stabilization, LDES-ready regulation) to de-risk vanadium for grid storage and low-carbon infrastructure. This study also discusses supply chain concentration and price volatility, and outline circular-economy pathways and decarbonization policy levers relevant to the EU’s green energy transition. Full article

The design of the chemical structure of ion-conductive membranes is critical to enhance proton/vanadium ion selectivity and the performance of vanadium redox flow batteries (VRFBs). Herein, camphorsulfonic acid is proposed as a novel proton-conductive group and grafted on polybenzimidazole (PBICa). The pendant sulfonic acid group on the end of the grafted side chains is flexible to promote the aggregation of ionic clusters at even a relatively low ion-exchange capacity (IEC) of 2.14 mmol g⁻¹. The formation of these high-quality clusters underscores the remarkable efficacy of this structural strategy in driving nanoscale phase separation, which is a prerequisite for creating efficient proton-conducting pathways. The bulky and non-coplanar architecture of the camphorsulfonic acid group helps to increase the proportion of free volume compared with the conventional sulfonated polybenzimidazole, which not only promotes water uptake to facilitate proton transport but also exerts a sieving effect to effectively block vanadium ion permeation. The well-formed ionic clusters, together with the expanded free volume architecture, endow the membrane with both high proton conductivity (30.5 mS cm⁻¹) and low vanadium ion permeability (0.15 × 10⁻⁷ cm² s⁻¹), achieving excellent proton/vanadium ion selectivity of 9.85 × 10⁹ mS s cm⁻³, which is about 5.6-fold that of a Nafion 212 membrane. Operating at 200 mA cm⁻², the PBICa-based VRFB achieves an energy efficiency of 78.4% and a discharge capacity decay rate of 0.32% per cycle, outperforming the Nafion 212-based battery (EE of 76.9%, capacity decay of 0.79% per cycle). Full article

Accurate and real-time state of charge (SOC) monitoring is critical for the safe, efficient, and stable long-term operation of vanadium redox flow batteries (VRFBs). Traditional monitoring methods are susceptible to errors arising from side reactions, cumulative drift, and electrolyte imbalance. This study develops a non-invasive optical sensor module for the negative electrolyte (anolyte), utilizing the favorable spectral properties of V(II)/V(III) ions at 850 nm for real-time SOC tracking. A fifth-order polynomial model was employed for calibration, successfully managing the non-linear optical response of highly concentrated electrolytes and achieving exceptional accuracy (adjusted R² > 0.9999). The optical sensor reliably tracked capacity degradation over 50 galvanostatic cycles, yielding a degradation curve that showed a high correlation with the conventional coulomb counting method, thus confirming its feasibility for assessing battery’s state of health. Contrary to initial expectations, operating at higher current densities resulted in a lower capacity degradation rate (CDR). This phenomenon is primarily attributed to the time-dependent nature of parasitic side reactions. Higher current densities reduce the cycle duration, thereby minimizing the temporal exposure of active species to degradation mechanisms and mitigating cumulative ion imbalance. This mechanism was corroborated by physicochemical analysis via UV-Vis spectroscopy, which revealed a strong correlation between the severity of spectral deviation and the CDR ranking. This non-invasive optical technology offers a low-cost and effective solution for precise VRFB management and preventative maintenance. Full article

Redox flow batteries (RFBs) are an emerging class of large-scale energy storage devices, yet the commercial benchmark—vanadium redox flow batteries (VRFBs)—is highly constrained by a modest open-circuit potential (1.26 V) while posing an expensive and volatile material procurement costs. This review focuses on recent progress in diversifying redox-active species to overcome these limits, highlighting chemistries that increase overall cell voltage, energy density, and efficiency while maintaining long cycle life and safety. The study dwells deeper into manganese-based systems (e.g., Mn/Ti, Mn/V, Mn/S, M/Zn) that leverage Mn’s high positive potential while addressing Mn(III) disproportionation reactions; iron-based hybrids (Fe/Cr, Fe/Zn, Fe/Pb, Fe/V, Fe/S, Fe/Cd) that exploit the low cost, and its abundance, along with membrane and electrolyte strategies to prevent the potential issue involving crossover; cerium-anchored catholytes (Ce/Pb, V/Ce, Eu/Ce, Ce/S, Ce/Zn) that deliver high operational voltage by implementing an acid-base media, along with selective zeolite membranes; and halide systems (Zn–I, Zn–Br, Sn–Br, polysulfide–bromine/iodide) that combine fast redox kinetics and high solubility with advances such as carbon-coated membranes, bromine complexation, and ambipolar electrolytes. Across these various families of RFBs, the review highlights the modifications made to the flow-fields, membranes, and electrodes by utilizing a zero-gap serpentine flow field, sulfonated poly(ether ether ketone) (SPEEK) membranes, carbon-modified and zeolite separators, electrolyte additives to enhance the voltage (VE%), and thereby energy (EE%) efficiency, while reducing the overall system cost. These modifications to the existing RFB technology offer a promising alternative to traditional approaches, paving the way for improved performance and widespread adoption of RFB technology in large-scale grid-based energy storage solutions. Full article