Kalyan Sundar Krishna Chivukula and
Yansong Zhao
*
Department of Safety, Chemistry and Biomedical Laboratory Sciences, Western Norway University of Applied Sciences (HVL), 5063 Bergen, Norway. E-mail: yansong.zhao@hvl.no; yansong.zhao2004@gmail.com
First published on 17th July 2025
Vanadium redox flow batteries (VRFBs) have emerged as a promising contenders in the field of electrochemical energy storage primarily due to their excellent energy storage capacity, scalability, and power density. However, the development of VRFBs is hindered by its limitation to dissolve diverse vanadium salts in the aqueous solution without significantly impacting the viscosity and thereby, the operational efficiency. To address this challenge, a novel aqueous ionic-liquid based electrolyte comprising 1-butyl-3-methylimidazolium chloride (BmimCl) and vanadium chloride (VCl3) was synthesized to enhance the solubility of the vanadium salt and aid in improving the efficiency. The synthesized novel electrolyte combination showcased a maximum theoretical energy density of approximately 44.24 Wh L−1, a dynamic viscosity of 36.62 mPa s along with a stable potential window of approximately 1.8 V, and an ionic conductivity of 0.201 S cm−1 at room temperature. Furthermore, the aqueous ionic-liquid based VRFB demonstrated an appreciable coulombic efficiency and capacity retention of greater than 85% at a discharge current of 5 mA. The maximum achievable concentration utilizing deionized water was obtained to be 2 M, which can be significantly enhanced by utilizing various component combinations of organic solvents, and ionic liquids to unlock the full potential of VRFBs. This novel electrolyte composition provides a promising pathway for improving the energy density and operational efficiency of VRFBs, paving the way for advanced energy storage solutions.
In contrast to these traditional ion-based batteries, redox flow batteries (RFBs) present an innovative solution to overcome these limitations.8–10 A key advantage of RFBs11 is that their energy storage capacity can be scaled independently i.e., by increasing the volume of the liquid electrolytes which are commonly known as catholyte and anolyte. Amongst the other features, this unique ability positions RFBs as a versatile and scalable alternative to traditional battery technologies in the grid-scale energy storage.
At the core of RFB operation is the separation of energy storage and power generation functions, which are independent of each other. The liquid electrolytes i.e., the anolytes and catholytes, are stored externally in a tanker and pumped through a cell stack containing current collectors, porous electrodes, and an ion-exchange membrane. The membrane facilitates ion transport between the anolyte and catholyte, ensuring efficient electrochemical redox reactions, and a continuous energy storage and release as shown in Fig. 1.
Among the various types of RFBs, vanadium redox flow battery (VRFB) stands out for its ability to eliminate cross-contamination between electrolytes, a common issue in other flow battery chemistries which induces self-discharge of the device. By utilizing vanadium as salt in both the anolyte and catholyte, VRFBs significantly enhance their energy storage capacity and operational stability, making them a leading contender for large-scale energy storage solutions.
In VRFBs, energy storage is achieved through the use of vanadium ions in different oxidation states ranging from +2 to +5. The positive electrolyte (catholyte) contains vanadium in the +4 (VO2+) and +5 (VO2+) oxidation states, while the negative electrolyte (anolyte) contains vanadium in the +2 (V2+) and +3 (V3+) states as illustrated in the Fig. 1. This all-vanadium system prevents cross-contamination, a common issue in other redox flow battery chemistries, such as iron–chromium (Fe–Cr) and bromine–polysulfide (Br–polysulfide) systems.
In a typical VRFB, vanadyl sulfate (VOSO4) is dissolved in sulfuric acid (H2SO4) and water to form the electrolyte. During discharge, vanadium ions at the electrodes undergo electrochemical reactions, where the carbon felt or graphite electrodes facilitate electron transfer to the external circuit, and protons move across a cation-exchange membrane (e.g., Nafion) to balance charge in the system. The key half-cell reactions and their respective standard potentials (versus the standard hydrogen electrode, SHE) are as follows:
Anode reaction (discharge):
V2+ ↔ V3+ + e−, E0 = −0.26 V vs. SHE |
Cathode reaction (discharge):
VO2+ + H2O ↔ VO2+ + 2H+ + e−, E0 = 1.00 V vs. SHE |
The overall open circuit potential (OCP) of the VRFB is determined by the potential difference between the cathode and anode reactions, yielding the following,
VO2+ + H2O + V3+ ↔ VO2+ + V2+ + 2H+, EOCP = 1.26 V |
The key to enhancing the energy storage capacity in a VRFB is increasing the concentration of dissolved vanadium salt in the electrolyte with the help of a variety of solvents ranging from aqueous, non-aqueous, and ionic liquids etc. In this regard, ionic liquids (ILs) have emerged as a promising class of solvents that can significantly improve electrolyte performance in VRFBs by significantly enhancing the operating temperature ranges, electrochemical stability window, efficiency, and the concentration of vanadium salt in the electrolyte.
However, limited studies have explored the use of ionic liquids in VRFBs despite of their unique chemical and physical properties.12–16 As mentioned earlier, traditional VRFBs often rely on aqueous sulfuric acid-based electrolytes, but these are limited by the low to moderate solubility of vanadium ions and the imminent risk of thermal precipitation of vanadium pentoxide (V2O5) at elevated temperatures, which restricts their operating window to 10–40 °C. Overcoming this, ionic liquids offer an attractive alternative primarily due to their ability to operate over a wider temperature range, their chemical stability, low volatility, and tuneable physical properties such as viscosity and conductivity.
In a study performed by Nikiforidis et al.15 a protic ionic liquid (PIL) namely PyrrH+CH3SO3− was formulated and synthesized, which was introduced as a solvent for vanadium-based electrolytes in VRFBs, to access its impact on the electrochemical performance of the battery. By employing PILs, researchers were able to dissolve up to 6 mol L−1 of vanadyl sulfate (VOSO4) – a 2.5 times increase in the concentration of vanadium electrolyte when compared to the maximum achievable concentration with sulfuric acid with a significant drawback of higher viscosity, and lower conductivity. The PIL-based VRFBs demonstrated thermal stability across a wide range of operating temperatures (−20 °C to 80 °C), maintaining chemical stability over several weeks. Further, electrochemical tests revealed quasi-reversible redox reactions at both the anolyte and catholyte, comparable to traditional sulfuric acid electrolytes, while achieving an open circuit potential (OCP) of 1.39 V. Moreover, To investigate the influence of protic ionic liquid under the cyclic charge–discharge conditions, a redox flow battery comprising 0.5, 2.5 and 4 mol L−1 vanadium(IV) was dissolved in 1.5 mol L−1 PIL, which is then compared to a 1.5 mol L−1 H2SO4 electrolyte. The VRFB's electrolyte incorporated with PIL showcased an excellent cyclic stability (150+ cycles) along with energy and coulombic efficiencies of 65% and 93% respectively with a nominal capacity of 1250 mAh at a current density of 60 mA cm−2. This advancement underscores the potential of PILs to dramatically enhance the performance of VRFBs.
Further exploration into non-aqueous redox flow batteries (NARFBs) utilizing ionic liquids has also demonstrated promising results. One such study formed by Bahadori et al.16 evaluated the performance of non-aqueous vanadium redox flow systems based on vanadium acetylacetonate (V(acac)3) in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4mim][NTf2]) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([C4mpyr][NTf2]). These IL-based systems yielded a cell potential of 2.2 V, significantly higher than the currently utilized aqueous systems, with coulombic efficiencies ranging from 88 to 92% over 50 cycles. Despite the higher viscosity of the ILs, which can slow mass transport, the systems showed quasi-reversible redox behaviour similar to the PILs utilized in the previous study, for the vanadium redox couples. This study highlighted the ability of ILs to provide a broader electrochemical window, allowing for greater energy density and wider operational flexibility compared to traditional aqueous electrolytes.
Overall, these studies establish ionic liquids as a highly versatile and effective alternative to conventional aqueous electrolytes in VRFBs. By leveraging the tuneable properties of ILs, VRFBs can achieve higher vanadium solubility, better thermal stability, and enhanced electrochemical stability windows, making them ideal candidates for next-generation energy storage technologies.
Moreover, ionic liquids have found widespread use in a variety of energy storage devices, including fuel cells, lithium-ion batteries, and supercapacitors, due to their ability to enhance performance. One ionic liquid that stands out is 1-butyl-3-methylimidazolium chloride (BmimCl). In lithium-ion batteries, BmimCl has been incorporated into hybrid gel polymer electrolytes (HGPEs) consisting of PMMA–PLA doped with LiTFSI, leading to significant improvements in ionic conductivity and electrochemical stability.17 By interacting with the polymer matrix, BmimCl facilitates enhanced ion transport across the electrolyte region, resulting in higher charge carrier mobility and improved battery performance. The electrolyte consisting of 80% PMMA:20% PLA:20 wt% LiTFSI:15 wt% BmimCl showcased an extremely high ionic conductivity viz. 1.63 × 10−3 S cm−1 at room temperature. Furthermore, the electrochemical stability window of the thus-formed electrolyte was evaluated at room temperature, and it was 3.4 V vs. Li/Li+.
In the case of supercapacitors, BmimCl-based ionogels have shown excellent mechanical strength, ion conductivity, and the ability to perform at high temperatures, making them ideal for use in all-solid-state super capacitors devices.18 A notable combination mentioned in the study was of BmimCl with chitosan and hydroxyethyl methacrylate (HEMA), which forms an ionogel that not only recovers its mechanical strength after compression but also demonstrates superior electrochemical behaviour at elevated temperatures.
BmimCl has also proven to be a valuable component in the electrolytes in fuel-cells,19 particularly when used to enhance the performance of proton-conducting polymer electrolytes. Studies have shown that doping poly(vinyl alcohol) (PVA)-based membranes with BmimCl improves both the ionic conductivity (5.74 mS cm−1) and thermal stability (250 °C) of the fuel cells, resulting in higher efficiency and a maximum power density of 18 mW cm2 at room temperature. Finally, BmimCl has been successfully applied in rechargeable iron-ion batteries,20 where its high stability, non-volatility, and superior ionic conductivity make it a safer and more efficient alternative to traditional organic electrolytes. This makes BmimCl a versatile candidate for improving the performance of various next-generation energy storage technologies.
In this study, 1-Butyl-3-Methylimidazolium Chloride (BmimCl) is utilized in combination with Vanadium Chloride (VCl3), and de-ionized (DI) water, to induce a common ion in comparison with the ionic liquid, to develop an aqueous ionic liquid-based VRFB. This novel electrolyte formulation demonstrated superior cyclic charge–discharge performance at room temperature along with an optimum viscosity of the liquid electrolyte, and a broad electrochemical stability window. The replacement of BmimCl with H2SO4 offered a much safer, and an efficient alternative while maintaining high efficiency, and electrochemical performance which has not been explored as a potential electrolyte for VRFBs.
This manuscript focuses on several key aspects, including the preparation of a novel aqueous ionic liquid based electrolyte for VRFBs, and their comprehensive characterization utilizing a wide-range of techniques such as Fourier-transform infrared spectroscopy (FTIR), viscometry, density measurement, cyclic voltammetry (CV), and cyclic charge–discharge performance tests to evaluate the physical and chemical properties of the electrolyte system. These characterizations provide a detailed understanding of the enhanced electrochemical performance and stability offered by BmimCl in VRFB applications, highlighting its potential as a viable and improved alternative to traditional acid-based systems by promoting green-chemistry.
Further, the ethanol present in the solution was carefully removed utilizing a rotavapor system the next day. During this process, the pressure was maintained below 10 mbar at a temperature of 95 °C primarily to enhance the removal of ethanol, and the rotation speed was set at 120 rpm to facilitate a uniform solvent removal.
The removal process was monitored by measuring the weight of the solution before and after the treatment. The procedure was continued until there were no visible droplets of ethanol condensed in the collector tank. Once the ethanol was fully removed, the resulting thick and viscous mixture was verified to identify any residual presence of ethanol using Nuclear Magnetic Resonance (NMR). 1H Nuclear Magnetic Resonance (1H NMR) spectroscopy was employed to assess the chemical composition and purity of the synthesized ionic liquid. The measurements were performed on a 600 MHz spectrometer using DMSO as the solvent. The recorded spectrum displayed the following chemical shifts (δ, in ppm): δ 9.36 (s, 1H), 7.78 (d, J = 42.7 Hz, 2H), 4.17 (t, J = 6.6 Hz, 2H), 3.86 (s, 3H), 1.75 (p, J = 6.6 Hz, 2H), 1.24 (h, J = 6.9 Hz, 2H), and 0.89 (t, J = 7.1 Hz, 3H).
No peaks corresponding to the residual ethanol in the BmimVCl4 solution were observed. Ethanol typically displays a triplet around δ 1.2 ppm (–CH3) and a quartet near δ 3.6 ppm (–CH2–OH), which are clearly absent in the obtained spectrum. Additionally, a small signal at δ ∼3.3 ppm was attributed to water present in the deuterated DMSO (DMSO-d6), and not related to the sample. On conforming the purity of the electrolyte, the sample was diluted, and homogenized with deionized water to synthesize 1.3 mol L−1 BmimVCl4 aqueous solution.
A total of 30 mL of this solution was prepared and subsequently divided into two equal portions of 15 mL each. These portions were designated for use as the catholyte and anolyte in the VRFB. This careful preparation ensures the homogeneity and accuracy of the electrolyte solution, which is critical for optimal battery performance.
Two separate electrolyte reservoirs containing the synthesized BmimVCl4 electrolyte solution, designated as the catholyte and anolyte, are utilized for each half-cell of the battery, through which the redox reactions occurs while charging and discharging. Tubes connect the reservoirs holding the liquid electrolyte to the flow cell, and two positive displacement peristaltic pumps are employed to circulate the electrolytes continuously through the flow cell, ensuring that the redox-active species reach the porous carbon felt electrodes in the flow cell. The flow rate of the catholyte, and the anolyte solutions has been fixed at 20% of the overall RPM of the pump, which corresponds to a mass flow rate of 0.21 g s−1.
The experimental setup is carefully arranged to maintain a stable flow of electrolyte with the help of a positive displacement peristaltic pumps. The system is tested for a series of charge and discharge cycles with varying voltage, current conditions to assess the overall efficiency of VRFB.
The programme followed during the charge and discharge cycles is as outlined below,
(1) Rest period (30 seconds): at the start of the testing cycle, the system is allowed to rest for 30 seconds prior to the first charge cycle, to ensure that the open-circuit potential (OCP) is as close to zero as possible. This process aids in eliminating any residual charges in the system, and ensures an accurate efficiency measurement.
(2) Charging at constant current (25 mA): the first charging step is performed at a constant current of 25 mA until the voltage of the cell reaches 1.5 V. The voltage is restricted to 1.5 V to prevent the electrolysis of water in the aqueous ionic liquid based electrolyte, which could otherwise negatively impact battery performance by releasing hydrogen, and oxygen gases at the anode, and cathode respectively, and cause significant performance degradation over time.
(3) Charging at constant voltage (1.5 V): on reaching the potential difference of 1.5 V, the charging process now proceeds in a constant voltage regime which is significantly slower as compared to a constant current regime. At a constant voltage of 1.5 V the battery charges till the capacity reaches 100 mAh. This ensures that an adequate amount of charge is stored for the subsequent efficiency calculations and performance evaluation throughout the cycles.
(4) Rest period (10 seconds): once the charging phase is complete i.e., the CC and CV regimes, the system proceeds to rests for 10 seconds, which allows the cell potential to stabilize, and the discharge process is initiated. The resting cell voltage is typically around 1.3 V and is recorded for later analysis.
(5) Discharge at constant current (1 mA): the discharge phase begins at a constant current of 1 mA until the voltage reaches to 0.5 V. This controlled discharge at low discharge currents allows for a steady release of stored energy from the battery.
(6) Discharge at constant voltage (0.5 V): once the voltage reaches 0.5 V, the discharge continues at the constant voltage of 0.5 V until the current drops below 0.1 mA. This step ensures the battery is fully discharged, allowing for accurate energy efficiency calculations.
(7) Cycle repetition: this entire charge–discharge process is repeated for approximately 10 cycles to measure the efficiency and performance variation of the VRFB with cycle number. This is essential for determining the durability and operational stability of the battery over time.
Unless otherwise specified, throughout the manuscript, the following programme has been utilized to charge and discharge the VRFB, to measure its electrochemical characteristics.
The measurements were conducted over a wide range of temperatures from 25 °C to 50 °C with a 5 °C step size, and at a measurement angle of 45° to account for the solution's behaviour across typical operating conditions. The temperature-dependent viscosity data provided valuable insights into the solution's flow properties, ensuring it remains within the optimal range for effective performance in the VRFB.
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Fig. 3 The cyclic voltammetry of 1.3 M BmimVCl4 at a scan rate of 0.01 V s−1, and voltage ranges −0.9 V to 0.9 V consisting of 20 cycles. |
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Fig. 4 The cyclic voltammetry of 1.3 M BmimVCl4 at a scan rate of 0.01 V s−1, and voltage ranges −0.67 V to 0.67 V. |
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Fig. 5 The cyclic stability of 1.3 M BmimVCl4 at a scan rate of 0.01 V s−1, and voltage ranges −0.67 V to 0.67 V. |
Additionally, in the Fig. 3, two more smaller oxidation and reduction peaks can be observed in the high-voltage zones. These 4 peaks suggest the reduction and oxidation of vanadium from +2 to +3, and +4 and +5. Furthermore, the theoretical open-circuit potential (OCP) of the VRFB is approximately 1.3 V (according to the thermodynamic constraint), and the experimentally obtained one is 1.27 V, which aligns closely with the voltage measured at the battery terminals when fully charged till 1.5 V. This agreement indicates the completion of oxidation and reduction reactions, confirming the reversibility of the electrochemical processes in the system.
Moreover, in order to evaluate the cyclic stability of the synthesized VRFB, a CV test has been conducted for approximately 255 cycles at a scan rate of 0.01 V s−1 between the voltage ranges −0.67 V to 0.67 V as illustrated in the Fig. 5. This denotes a safe working potential of approximately 1.5 V, till which the galvanostatic charge–discharge tests have been performed. Furthermore, the peaks current and voltage variation at various scan rates ranging from 0.01 to 0.05 V s−1 have been recorded, and illustrated in the Fig. 6.
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Fig. 7 The variation of imaginary, and the real impedance with frequencies ranging from 0.01 Hz to 200 KHz. |
Element | Fitted value | Unit | Error (%) |
---|---|---|---|
R1 | 21.28 | Ω | 0.596 |
R2 | 7.151 | Ω | 2.560 |
C1 | 15.58 | μF | 7.112 |
W1 | 0.023 | kΩ | 0.916 |
Chi-squared | 0.0006 | Iterations | 25 |
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Fig. 9 The LSV graph obtained for the electrolyte to measure its stability window, performed at a scan rate of 0.001 V s−1. |
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Fig. 10 The variation in the dynamic viscosity of the anolyte, catholyte, and the mixed solution after the 20th cycle from temperatures ranging from 298 K to 323 K. |
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Fig. 11 The variation in the density of the liquid electrolyte viz. 1.3 M BmimVCl4 from temperatures ranging from 298 K to 323 K. |
BmimVCl4 concentration (M) | Measured pH | Calculated [H+]/mol L−1 |
---|---|---|
1.0 | 1.065 | 8.6 × 10−2 |
1.3 | 0.888 | 1.3 × 10−1 |
1.5 | 0.780 | 1.6 × 10−1 |
2.0 | 0.595 | 2.5 × 10−1 |
The incorporation of BmimCl to VCl3, results in the formation of chloro-metalate anions,22 which can be described as,
BmimCl + VCl3 → Bmim+ [VCl4]− |
The formed [VCl4]− reacts with H2O in order to form the following,
[VCl4]− + H2O → VO2+ + 4Cl− + 2H+ |
Upon the addition of DI water to reduce the viscosity of the 2.0 M BmimVCl4 solution, the pH has been altered, and the for the 1.3 M solution, the pH obtained was 0.888. The H+ ions aids in maintaining the acidic nature of the electrolyte, thereby suppressing the precipitation of V5+, and moreover helps in maintaining electroneutrality by transporting across the proton exchange membrane – NAFION. VCl3 acts as a Lewis acid (e− pair acceptor), and the Cl− from the BmimCl acts as a Lewis base (e− pair donor), and the reaction between them leads to the formation of chloro-metalate anions as mentioned above. The formed [VCl4]− complex is stabilised by the Bmim+ in the electrolyte solution. This is similar to the behaviour exhibited by AlCl3, FeCl3 in the presence of BmimCl. Further, UV-Vis studies have been conducted to assess the oxidation states exhibited by the vanadium in the solution in the form of vanadium complexes, and the obtained data is illustrated in the Fig. 12.
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Fig. 12 The UV-Vis data of 1 M, and 0.1 M solution of BmimVCl4 in the presence of DI water as solvent. |
If the reactions proceeded in the way described above, upon the addition of DI water, V4+ must be formed viz. VO2+, and it has a peak around 760 nm.23,24 However, the 1 M solution of BmimVCl4 showcased a broad range of absorption ranging from 380–790 nm, indicating the co-existence of vanadium in 3 different oxidation i.e., +3, +4, and +5 in the form of chloro-metalate complexes on the reaction with BmimCl. Due to the high concentration of H+ ions for the solutions greater than or equal to 1 M, the formation of VO2+ is inhibited as the reactions tends to move towards the reactants side to maintain the equilibrium according to the Le Chatelier's principle, favouring the formation of vanadium complexes rather than V4+, thus, leading to a broad range of absorption rather than a single peak at 760 nm. However, upon the addition of water i.e., diluting the solution to 0.1 M, the concentration of H+ ions goes down drastically reducing the pH of the solution, and thereby favouring the production of V4+, which oxides to form V5+ in the presence of oxygen, and this is evident from the singular peak obtained at 420 nm indicating the presence of V5+ in the solution. To assess the impact of the synthesized electrolyte on the electrochemical performance of the redox flow battery, 1.3 M solution has been selected primarily due to its optimal viscosity, and pH values as compared to the higher concentrations. The charge–discharge characteristics of the VRFB utilizing BmimVCl4 as the liquid electrolyte, are illustrated in Fig. 13–15. These figures provide insights into the charge and discharge capacity, efficiency, and mid voltage variation over multiple cycles. Fig. 13 depicts the variation in charge and discharge capacities measured in mAh as a function of cycle number, wherein the charging capacity of the VRFB remains constant at 100 mAh throughout the preliminary test to maintain a consistency in the obtained results.
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Fig. 13 The variation of charge, and the discharge capacities of the VRFB with cycle number, wherein, the capacities are measured in mAh. |
While the discharge capacity initially fluctuates between 81 mAh and 86 mAh during the initial cycles, after the third cycle the discharge capacity stabilizes with a mid-voltage of approximately 0.7 V, as depicted in the Fig. 14, indicating that the system has reached its stable working operational condition. As illustrated in the Fig. 15, the capacity retention of the VRFB over the different cycles alters around 83% throughout the cycles, however, the voltage efficiency (VE) lingers around 50% signifying the high resistance in the battery, resulting in significant drop of the nominal potential. The coulombic efficiency (CE) retains around 80%, and the energy efficiency (EE) remains around 45%. The following parameters were calculated as follows,
EE = CE × VE |
Following the third cycle, the capacity retention stabilizes and remains consistently above 80% in subsequent cycles, confirming the reliable and stable operation of the VRFB. Further, the charging capacity has been increased to 200, 500, and 750 mAh to evaluate its influence on the discharge characteristics of the VRFB under higher discharge currents and capacities. On charging the VRFB to 200 mAh, the corresponding discharge capacity was achieved to be 182 mAh with a lower cut-off potential as 0 V, resulting in an efficiency of 91.43%, at a mid-voltage of 0.6585 V, and a discharge current of 1.5 mA. In order to obtain the maximum energy storage capacity, the battery has been further charged till 500 mAh, and 750 mAh, to evaluate its efficiency variation, and to calculate the energy density of the battery. The corresponding discharge capacities were 450 mAh, and 543.61 mAh, with efficiencies of 90% and 72.13% respectively.
As mentioned earlier, the catholyte, and the anolyte volume utilized is 15 mL, however, for the energy density calculations, 12 mL of each electrolyte has been utilized to obtain the results. The specific capacity calculated based on the highest discharge capacity was 22.6504 Ah L−1. This specific capacity is achieved with an efficiency greater than 70% at a discharge current of 5 mA, which is a favourable performance for VRFBs utilizing ionic liquid electrolytes for grid-scale energy storage solutions. Moreover, the energy density can be evaluated with the help of the obtained specific volumetric capacity and the nominal working potential of the VRFB as, 22.6504 Ah L−1 × 0.3206 V = 7.2617 Wh L−1, which is around approximately 17% of the maximum achievable theoretical energy density of 44.24 Wh L−1. The theoretical energy density has been calculated as follows,
The discrepancy obtained in the resulting value of energy density is primarily owed to two factors – lower value of discharge capacity, and nominal voltage during the discharge, which can be linked to the availability of V5+ during the discharge i.e., SOC, and the mass transport resistance induced by the synthesized electrolyte. As mentioned earlier, the viscosity of the electrolyte is 36.62 mPa s at room temperature, which is significantly higher as compared to the commercialised redox flow battery electrolytes i.e., VOSO4 in H2SO4 and DI water. The high viscosity hinders the mass transport, and thereby results in an elevated resistance for the electrolyte solution as evaluated from the EIS studies. Furthermore, as observed from the VE data, there is a significant loss i.e., approximately 50%, primarily owing to the ohmic drops, and the mass transport overpotential which are in turn related to the viscosity of the electrolyte. Due to the low operational potential, the energy density of the battery is significantly reduced. Even though, subsequent to increasing the nominal potential during from 0.3 V to 1.0 V (theoretically, for the sake of evaluation), the energy density of the flow battery can reach 22 Wh L−1, which is almost 40% lower as compared to the theoretical energy density, and this can be attributed to the SOC of the battery i.e., the theoretical assumption of 100% V5+ ions, must be achieved experimentally viz. a SOC of 100%. The future works includes reducing the viscosity of the electrolyte, and thereby suppressing the resistances in the electrolyte and enhancing the nominal discharge potential to achieve an energy density value as closer to the theoretically evaluated one.
Moreover, in comparison to a commercialised vanadium redox flow battery, the synthesized flow battery based on ionic liquid excels in the replacement of acid–base (H2SO4, HCl) systems, with a novel, green ionic liquid based electrolyte. This aligns with the green chemistry principles and address safety, environmental, and material degradation concerns that limit long-term stability in the commercial VRFBs. While ionic liquid systems offer unique benefits such as a broader electrochemical window (up to 1.8 V as demonstrated from the Fig. 3, in spite of utilizing DI water as solvent) they also introduce huge challenges on the research point of view, such as high viscosity viz. 36.62 mPa s, which increase the mass transport resistance and reduce the VE, and subsequently EE. Consequently, although the flow battery achieves a CE exceeding 85%, the VE remains below 60%. Furthermore, commercial VRFBs typically operate at a current density of 30–50 mA cm−2, while the current ionic-liquid based system is optimized for up to 1–5 mA cm−2. In terms of the energy density, the conventional systems25 demonstrate values between 12–120 Wh L−1, and the achieved value of 7.26 Wh L−1 is a promising starting point considering this as a green system.
Additionally, on the completion of evaluating the charge–discharge characteristics of the VRFB, the NAFION membrane has been removed from the battery to analyse its condition i.e., to identify any ruptures, and the resulting images are showcased in Fig. 16. From the figure, it can be implicated that there is no damage to the membrane, and it is resistant to the synthesized formulation of aqueous ionic-liquid based electrolyte.
Furthermore, as mentioned earlier, the energy density of the VRFB can be significantly enhanced by further improving the concentration of VCl3 in the electrolyte while reducing the viscosity. As per the performed experiments, the maximum achievable concentration of vanadium salt utilizing BmimCl as the IL and water as solvent, was approximately 2 mol L−1, which can further be enhanced by the utilizing of organic solvents to reduce the viscosity and increase the concentration of vanadium salt in the electrolyte which can aid significantly in improving the performance of the battery, which will be focused as the future work.
The synthesized electrolyte can theoretically achieve an energy density of 44.24 Wh L−1, with favourable properties such as a dynamic viscosity of 36.62 mPa s at room temperature, an ionic conductivity of 0.201 S cm−1, and a stable potential window of approximately 1.5 V for numerous cycles. To evaluate the stability of the synthesised electrolyte, more than 200 cycles of cyclic charge–discharge has been performed. Moreover, the VRFB employing this novel electrolyte demonstrated superior cycling performance, with coulombic efficiency (CE) and capacity retention exceeding 80% at a discharge current of 5 mA. However, the formulations utilized in the VRFB, showcased poor voltage efficiency (VE) and energy efficiency (EE) owing to its ohmic, and mass-transport resistances offered by the electrolyte. These results indicate that the combination of ionic liquids and aqueous systems can overcome the solubility and viscosity limitations of conventional aqueous electrolytes, unlocking higher energy densities and greater operational stability.
The findings of this work underscore the potential of ionic-liquid based electrolytes to revolutionize VRFB technology by enhancing energy density and operational efficiency. Further exploration of organic solvents and ionic liquid combinations could lead to the development of next-generation VRFBs with higher vanadium concentrations and improved charge–discharge characteristics. This research provides a foundational step toward advanced energy storage solutions, paving the way for more efficient and sustainable grid-scale energy storage systems.
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