Flow Battery Research Articles

Statistical Analysis of Levelized Round Trip Cost of Grid Scale Electrical Energy Storage in Batteries with Different Chemistries

Electrical energy storage is a crucial component of the clean energy transition for integrating high share of renewable electricity generators into the supply mix. In this study, the round-trip costs of grid scale electrochemical energy storage from 2 up to 24 hours for peak power ratings of 1 MW and 10 MW in lithium-ion LFP, lithium-ion NMC, Pb-acid and vanadium redox flow batteries are compared using their currently projected techno-economic characteristics for year 2030. A statistical approach is used for estimating mean costs and quantifying the uncertainties in these estimates, since many of the techno-commercial features are still evolving and are uncertain. Using Monte Carlo simulations to derive the input parameters, the levelized round trip cost of energy storage is found to vary from Rs 10.73±0.77/kWh(e) to Rs 15.96±1.12/kWh(e) for Li-LFP batteries, Rs 14±1/kWh(e) to Rs 20.3±1.46/kWh(e) for Li-NMC batteries, Rs 19.1±1.39/kWh(e) to Rs 58.3±4.28/kWh(e) for Pb-acid batteries and Rs 18.7±1.37/kWh(e) to Rs 44.2±3.19/kWh(e) for Vanadium redox flow batteries, for the range of input values considered in this study. Through sensitivity analysis and calculation of correlation coefficients, the battery installed capital cost and useful lifetime are found to be the two most influential parameters affecting life cycle electrical energy storage cost.

Development of Tailored Hydrocarbon‐Based Pentablock Copolymer Membranes for Sodium‐Polysulfide Flow Batteries

AbstractLong‐duration energy storage (LDES) technologies are pivotal for the adoption of renewables like wind and solar. Non‐aqueous redox flow batteries (NARFBs) with a sodium‐polysulfide hybrid system feature high energy density independent of power density, yet face challenges with polysulfide shuttling. This study investigates a hydrocarbon‐based penta‐block copolymer membrane, Nexar, to mitigate crossover effects by balancing TFSI conversion and their crosslink density. The membranes are annealed to induce crosslinking for reducing electrolyte uptake and enhancing mechanical stability while demonstrating excellent ionic conductivity. The hydrocarbon‐based membranes address environmental concerns associated with perfluoroalkyl substances and improve the performance and durability of NARFBs. Our findings suggest that annealed Nexar membranes with tailored TFSI functionality offer a scalable, cost‐effective solution for enhancing the efficiency of high‐capacity energy storage systems, pivotal for grid integration of renewable sources.

Synergistic Effects of Energy Storage Systems and Demand-Side Management in Optimizing Zero-Carbon Smart Grid Systems

The urgent need to mitigate climate change and reduce reliance on fossil fuels has driven the global shift towards renewable energy sources (RESs). However, the intermittent nature of RESs poses significant challenges to the widespread adoption of Zero-Carbon Smart Grids (ZCSGs). This study proposes a synergistic framework to address this hurdle. It utilizes energy storage systems (ESSs) by comparing Vanadium redox flow batteries (VRFBs) and Lithium ion batteries (LIBs) to identify the most suitable option for ZCSGs, with precise models enabling robust performance evaluation. Moreover, an accurate demand-side management (DSM) strategy considering power elasticity to manage discrepancies between electricity load, RES generation, and ESS availability is introduced for estimating fair, dynamic tariffs. An advanced load and weather-forecasting strategy is introduced for improving grid planning and management. An advanced optimization algorithm enhances grid stability and efficiency. Simulations demonstrate significant reductions in carbon footprint, peak power demand, and reliance on fossil fuels. The study finds that VRFBs outperform LIBs in cost and security, and dynamic tariffs based on accurate DSM significantly reduce energy costs. This work explores the challenges and opportunities of this integrated approach, offering policy recommendations and future research directions for truly optimized ZCSG implementation.

Fluorine-Free Polynorbornene Membranes Based on a Sterically Hindered Pyridine for Vanadium Redox Flow Batteries

Fluorine-Free Polynorbornene Membranes Based on a Sterically Hindered Pyridine for Vanadium Redox Flow Batteries

Optimal Planning of Standalone Rural Microgrid With Effective Dispatch Strategies and Battery Technology

ABSTRACTMicrogrids are a viable substitute for traditional power systems because they may deliver cleaner, more dependable, affordable power with fewer losses. However, the microgrid's performance is impacted by the variable nature of renewable energy sources. Battery storage is a crucial component of microgrid planning since it defines the system's techno‐economic feasibility. A standalone rural microgrid is designed in the current study, employing three distinct battery types: lithium‐ion, lead acid, and zinc‐bromine flow. The suggested microgrid's techno‐economic analysis employs three distinct dispatch mechanisms, that is, cycle charging, load flow, and complete dispatch. The case study of the suggested framework is carried out in Lucknow (India). The system comprises PV/battery/wind energy system/diesel and battery. The simulation results suggest that the optimal system with the least electrification cost is 0.113 $/kWh using complete dispatch strategies and a zinc‐bromine battery. It has 206 kWh zinc‐bromine flow batteries, a 10 kW converter, a 20 kW PV, a 13‐kW diesel generator, and a Combined dispatch strategy. The system's net present cost per unit cost of energy is $40 275 and 0.113 $/kWh for the chosen region, respectively. Compared to the other two battery technologies for hybrid systems, the zinc‐bromine flow battery technology is also shown to be the most environmentally friendly. Among the three battery technologies available, zinc‐bromine flow is best used in a particular location's hybridized operation.

A High-Performance Polyimide Composite Membrane with Flexible Polyphosphazene Derivatives for Vanadium Redox Flow Battery.

A sulfonated polyimide, S-F-abSPI, with alkyl sulfonic acid side chains, and a polyphosphonitrile derivative, poly[4-methoxyphenoxy (4-fluorophenoxy) phosphazene] (PFMPP), were designed and synthesized. Composite modification of the S-F-abSPI membrane was carried out using PFMPP, resulting in the preparation of composite membranes with different composite ratios, which were then subjected to performance testing and characterization. Experimental results revealed a significant enhancement in the proton conductivity of the S-F-abSPI membrane, reaching 0.116 S cm-1, slightly higher than that of the N212 membrane. The S-F-abSPI/1% PFMPP composite membrane exhibited the optimal comprehensive performance, with a surface resistance as low as 0.54 Ω cm2, comparable to that of the N212 membrane. At a high current density of 200 mA cm-2 during charge-discharge, the composite membrane achieved a voltage efficiency (VE) of 83.12% and an energy efficiency (EE) of 81.95%. Cycling tests over 200 cycles demonstrated the composite membrane's excellent long-term cycling stability. The alkyl sulfonic acid side chains enhanced the proton conductivity of the membrane, while electrostatic potential distribution calculations indicated strong interactions between PFMPP and the base membrane, enhancing the membrane's mechanical strength, reducing vanadium ion permeability, and improving chemical stability and vanadium ion selectivity. This composite membrane holds promise for high-performance VRFB applications.

Preparation of Vanadium (3.5+) Electrolyte by Hydrothermal Reduction Process Using Citric Acid for Vanadium Redox Flow Battery

In this study, vanadium (3.5+) electrolyte was prepared for vanadium redox flow batteries (VRFBs) through a reduction reaction using a batch-type hydrothermal reactor, differing from conventional production methods that utilize VOSO4 and V2O5. The starting material, V2O5, was mixed with various concentrations (0.8 M, 1.2 M, 1.6 M, 2.0 M) of citric acid (CA) as the reducing agent and stirred for 60 min at 90 °C using a hot plate to ensure complete dispersion in the solution. The resulting solution was subsequently subjected to a hydrothermal reduction reaction (HRR) furnace at 150 °C for 24 h to generate vanadium (3.5+). The mixed states of the produced vanadium (3+) and vanadium (4+) were confirmed using UV-vis spectroscopy. The electrochemical properties of the electrolyte were investigated through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), revealing that the optimal concentration of the CA was 1.6 M. The current efficiency, energy efficiency, and voltage efficiency of the electrolyte produced via the HRR process was compared with that prepared using VOSO4 in charge and discharge experiments. The results demonstrate that the HRR process yields an enhanced electrolyte across all efficiency metrics produced through the given improved performance in all efficiencies. These findings indicate that the HRR process using citric acid can facilitate the straightforward preparation of vanadium (3.5+) electrolyte, making it suitable for large-scale production.

Optimizing Nonaqueous Sodium–Polysulfide Redox-Flow Batteries: The Role of Solvation Effects with Glyme Solvents

Optimizing Nonaqueous Sodium–Polysulfide Redox-Flow Batteries: The Role of Solvation Effects with Glyme Solvents

Hybrid solar photovoltaic-wind turbine system for on-site hydrogen production: A techno-economic feasibility analysis of hydrogen refueling Station in South Korea's climatic conditions

The South Korean government has an ambitious policy to roll out hydrogen-powered vehicles across the country with 2000 hydrogen refueling stations (HRSs) infrastructure by 2050. However, the country currently lacks sufficient HRS infrastructure. In this context, this study proposes and investigates the technoeconomic feasibility and performance assessment of an optimal hybrid renewable energy system integrated with a vanadium redox flow battery for on-site hydrogen production. The system is designed to refuel a fleet of 20 fuel cell electric vehicles at seven South Korean locations with distinct climates. Based on the typical daily hydrogen and electric load profile of the HRS, the capital expenditure, net present cost, operation expenditure, levelized cost of hydrogen and levelized cost of energy were estimated to be, $5.95 - $13.2 M, $8.93 - $19.4 M, 82,670–202,184 $/yr, 8.77–19.1 $/kg and 2.1–4.58 $kWh, respectively.

Recent Advances and Perspectives of Impurity Ions and Additives for the Electrolyte of Vanadium Redox Flow Battery

Recent Advances and Perspectives of Impurity Ions and Additives for the Electrolyte of Vanadium Redox Flow Battery

Selective ion transport through hydrated micropores in polymer membranes.

Ion-conducting polymer membranes are essential in manyseparation processes and electrochemical devices, including electrodialysis1, redox flow batteries2, fuel cells3 and electrolysers4,5. Controlling ion transport and selectivity in these membranes largely hinges on the manipulation of pore size. Although membrane pore structures can be designed in the dry state6, they are redefined upon hydration owing to swelling in electrolyte solutions. Strategies to control pore hydration and a deeper understanding of pore structure evolution are vital for accurate pore size tuning. Here we report polymer membranes containing pendant groups of varying hydrophobicity, strategically positioned near charged groups to regulate theirhydration capacity and pore swelling. Modulation of thehydrated micropore size (less thantwo nanometres) enables direct control over water and ion transport across broad length scales, as quantified by spectroscopic and computational methods. Ion selectivity improves in hydration-restrained pores created by more hydrophobic pendant groups. These highly interconnected ion transport channels, with tuned pore gate sizes, show higher ionic conductivity and orders-of-magnitude lower permeation rates of redox-active species compared with conventional membranes, enabling stable cycling of energy-dense aqueous organic redox flow batteries. This pore size tailoringapproach provides a promising avenue to membranes with precisely controlled ionic and molecular transportfunctions.

A flow battery cell testing facility for versatile active material characterization: Features and operations

Technological development plays a fundamental role in view of the successful realization of large Flow Battery (FB) systems. This work firstly presents the design, construction and commissioning of FB-Cell Testing Facility (FB-CTF), a bench for testing electrolytes, electrodes, membrane and cell configurations under controlled conditions. Several construction aspects related to the hydraulic system, power conditioning system, and flow battery management system are described in detail. FB-CTF has been conceived and built to accurately measure the main thermal, hydraulic, electric, and energy quantities which define the performance of FBs. A comprehensive experimental campaign has been carried out on FB-CTF to characterize some widely used electrodes and membranes for Vanadium FBs (VFBs), produced by some major manufacturers. The paper presents the developed testing protocols and the test results, specifically focusing on electrical and hydraulic characterization. In addition, a methodology using FB-CTF data in the prediction of the electric and hydraulic performance of large stacks is proposed. More generally, FB-CTF measurements can be used to address the design of industrial-scale FBs. FB-CTF can provide insights for the design of large flow battery systems, to help bridge the gap between academic research and industry.

Adenosine-Derivative Functionalized Carbon Nanotubes Considered as Catalysts for Vanadium Flow Batteries

Adenosine-Derivative Functionalized Carbon Nanotubes Considered as Catalysts for Vanadium Flow Batteries

Machine‐Learning‐Based Accurate Prediction of Vanadium Redox Flow Battery Temperature Rise Under Different Charge–Discharge Conditions

ABSTRACTAccurate prediction of battery temperature rise is very essential for designing efficient thermal management scheme. In this paper, machine learning (ML)‐based prediction of vanadium redox flow battery (VRFB) thermal behavior during charge–discharge operation has been demonstrated for the first time. Considering different currents with a specified electrolyte flow rate, the temperature of a kW scale VRFB system is studied through experiments. Three different ML algorithms; linear regression (LR), support vector regression (SVR), and extreme gradient boost (XGBoost) have been used for prediction. The training and validation of ML algorithms have been done by the practical dataset of a 1 kW 6 kWh VRFB storage under 40 , 45, 50, and 60 A charge–discharge currents and 10 L min−1 of flow rate. A comparative analysis among ML algorithms is done by performance metrics such as correlation coefficient (R2), mean absolute error (MAE), and root mean square error (RMSE). XGBoost shows the highest R2 value of around 0.99, which indicates its higher prediction accuracy compared to other ML algorithms used. The ML‐based prediction results obtained in this work can be very useful for controlling the VRFB temperature rise during operation and act as an indicator toward further development of an optimized thermal management system.

Front Cover: High‐performance Porous Electrodes for Flow Batteries: Improvements of Specific Surface Areas and Reaction Kinetics (ChemElectroChem 21/2024)

Front Cover: High‐performance Porous Electrodes for Flow Batteries: Improvements of Specific Surface Areas and Reaction Kinetics (ChemElectroChem 21/2024)

Pre-magnetization smashing hydrated vanadium ions to improve redox flow batteries performance

The vanadium redox flow battery (VRFB) has received extensive attention due to its intrinsic safety and high scalability. Currently, there are still deficiencies of low energy efficiency and higher unit capacity cost in VRFB energy storage. Continuously optimizing the battery performance through reducing electrode polarization losses is a necessary way to achieve efficient VRFB energy storage technology. In this study, a method of pre-magnetizing the electrolyte to improve the performance of the battery was proposed. A permanent magnet with an intensity of 0.9 T was used to pre-magnetize the vanadium-ion aqueous electrolyte before feed into the battery stack and working-on, it was found that the diffusion capacity of vanadium ions increased by 133.6 % after pre-magnetized even if the external magnetic field was removed. Meanwhile, both of the charge transfer and concentration polarization resistance of the electrode were reduced. The energy efficiency (EE) of the battery was increased by 6.4 % in the charge–discharge test at current density of 300 mA cm−2. The power density increased by 6.19 % with current density 400 mA cm−2 at most, and it prefers to continuously increase as current larger. The electrolyte pre-magnetization showed significant positive improvements on the electrode reaction kinetics and battery charge–discharge cycle.

A highly water-soluble phenoxazine quaternary ammonium compound catholyte for pH-neutral aqueous organic redox flow batteries

The pH-neutral aqueous redox flow battery (ARFB) is one of the most attractive flow batteries due to its non-corrosiveness, low-cost, and wider electrochemical stability window compared to those with acidic or alkaline electrolytes. However, there are few families of organic redox-active molecules available as catholyte materials for pH-neutral ARFBs. Herein, through incorporation of quaternary ammonium moiety into the redox-active phenoxazine nucleus, an organic catholyte material, N, N, N-trimethyl-2-(10H-phenoxazin-10-yl) ethan-1-aminium chloride (NEt-POZ) is achieved for pH-neutral ARFBs. The NEt-POZ has a high redox potential of 0.79 V versus SHE and rapid redox kinetics (0.23 cm s−1) as well as high water-solubility (∼2.6 M in H2O). Paired with a methyl viologen (MV) anolyte in the pH-neutral aqueous electrolyte, a viologen-phenoxazine ARFB full cell is assembled, which shows an open circuit voltage of ∼1.23 V. However, the results of long-term cycling experiments indicate low Coulomb efficiency and rapid declining capacity of the NEt-POZ catholyte. The mechanism analysis unveils that the unstable doubly oxidized tri-cations (NEt-POZ3+) formed via the disproportionation of radical di-cations (NEt-POZ2+) in solution readily react with chloride anions to form poly-chlorinated derivatives, which precipitate from the catholyte due to their poor water solubility, leading to a rapid decrease in capacity. When there is no chloride present in the electrolyte solution, highly reactive NEt-POZ3+ cations can interact with other counter-anions (such as sulfate and carbonate ions) and even water to form complex adducts.

Designer Fluorescent Redoxmer Self‐Reports Side Reactions in Nonaqueous Redox Flow Batteries

The state of health (SOH) is a critical measure for evaluating and predicting performance of redox flow batteries (RFBs). However, diagnosing SOH of RFBs is often challenging due to the overwhelming complexity of the electrolytes and associated electrochemical reactions. Designing active molecules or redoxmers that can autonomously exhibit property changes upon specific stimuli may provide a viable way for early diagnosis of SOH. Herein, a dimerized redoxmer, DGL‐N‐CH3, was designed and synthesized by linking blue‐green fluorescent monomers through a diglycolamide linker. While DGL‐N‐CH3 still maintains similar electrochemical behavior and strong fluorescence, we observe a unique side reaction when cycling DGL‐N‐CH3 in H‐cells, which leads to a side product, NHCH3‐BzNSN via linker cleavage. Interestingly, NHCH3‐BzNSN also emits fluorescence but at a longer wavelength. By taking advantage of this unique fluorescent change that corresponds to the growth of NHCH3‐BzNSN, we successfully established the capacity decay of DGL‐N‐CH3 H‐cell cycling, exemplifying a proof‐of‐concept self‐reporting redoxmer design towards in situ SOH monitoring.

Electrochemical investigations of decorated graphite felt electrodes with Nafion/TiO2 nanoparticles for vanadium redox flow battery: Improving electro-catalytic characteristics

The present study aimed to investigate the effect of Nafion/TiO2 nanoparticles as an electrocatalyst on the electrochemical behavior of graphite felt (GF) electrodes in a vanadium redox flow battery. Various electrochemical tests, including cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV), were conducted to assess the performance of these electrodes at different concentrations of nanoparticles (2-4 g L-1). Additionally, X-ray diffraction, Fourier transform infrared spectroscopy, and field emission scanning electron microscopy were employed to analyze the chemical composition, bonding, and morphology of the decorated electrodes, respectively. The CV results revealed several effects of TiO2 nanoparticles on the GF electrode, such as increased peak intensity and shifted peak sites. As the concentration of nanoparticles increased, the peak intensity rose by up to 44%. Moreover, the potentials of the decorated electrodes shifted towards the favorable side compared to the GF electrode, with changes ranging from 18 to 84%. Overall, the optimal concentration of TiO2 nanoparticles (3 g L-1) exhibited excellent electrode performance, characterized by the highest calculated diffusion coefficient, greater reversibility, enhanced electron transfer kinetics, improved stability, lower over-potential, and the lowest activation energy for redox reactions. EIS results demonstrated a significant decrease in polarization resistance (67.2-70.8%) for the decorated electrodes. Furthermore, LSV measurements indicated that the utilization of nano-electrocatalysts effectively inhibited hydrogen evolution at negative potentials.

The Effect of Electrochemical Ageing of Glassy Carbon Electrodes on VII-VIII and VIV-VV Kinetics

Electrode activity towards the negative and positive half-cell reactions of a vanadium flow battery were investigated. Cyclic voltammetry and electrochemical impedance spectroscopy were employed to monitor electrode activity of glassy carbon electrodes towards VII-VIII and VIV-VV redox reactions during electrochemical ageing through repeated anodic and cathodic treatments. Electrode activity is found to increase with number of treatment steps, showing little difference initially between anodised and cathodised electrodes. However, after several treatments, a potential-differentiated behaviour emerges, with distinct enhanced and inhibited states. For VII-VIII, anodised electrodes showed enhanced activity, while cathodised electrodes were inhibited. Conversely, for VIV-VV, cathodised electrodes had enhanced activity. In almost all cases, the activity is greater than that of an untreated electrode. Eventually, electrode activities stabilise in a steady-state region where activity depends on the final treatment potential rather than the number of steps. In this region, activity can be toggled reproducibly between enhanced and inhibited states. Therefore, it can be concluded that functional groups, rather than surface roughening or defect formation, are responsible for this toggling capability. Furthermore, for VIV-VV, steady-state activity levels and the number of treatment steps required to reach this region are found to be dependent on the upper and lower treatment potentials.