NEW AQUEOUS ORGANIC-BASED ELECTROLYTE FOR REDOX FLOW BATTERY

Abstract

Disclosed is an aqueous electrolyte for redox flow battery, including a compound of formula (I)

##STR00001##

and/or an ion of compound (I), and/or a salt of compound (I), and/or a reduced form of the anthraquinone member of compound (I), wherein: X.sup.1, X.sup.2, X.sup.4, X.sup.5, X.sup.6, X.sup.7 and X.sup.8 are independently selected from the group consisting of a hydrogen atom, a linear, cyclic or branched, saturated or unsaturated, optionally substituted, hydrocarbon group including from 1 to 10 carbon atoms, a OH group and a —O-A-R.sup.1 group, A representing a linear, cyclic or branched, saturated or unsaturated, optionally substituted, hydrocarbon group including from 1 to 10 carbon atoms; R.sup.1 representing COOH or SO.sub.3H; wherein one and only one of X.sup.1, X.sup.2, X.sup.4, X.sup.5, X.sup.6, X.sup.7 and X.sup.8 is OH, and wherein one and only one of X.sup.1, X.sup.2, X.sup.4, X.sup.5, X.sup.6, X.sup.7 and X.sup.8 is —O-A-R.sup.1.

Claims

1. An aqueous electrolyte for redox flow battery, comprising a compound of formula (I) ##STR00010## and/or an ion of compound (I), and/or a salt of compound (I), and/or a reduced form of the anthraquinone member of compound (I), wherein: X.sup.1, X.sup.2, X.sup.4, X.sup.5, X.sup.6, X.sup.7 and X.sup.8 are independently selected from the group consisting of a hydrogen atom, an halogen atom, an ether group of formula —O-A, a linear, cyclic or branched, saturated or unsaturated, optionally substituted, hydrocarbon group comprising from 1 to 10 carbon atoms, a OH group and a —O-A-R.sup.1 group, A representing a linear, cyclic or branched, saturated or unsaturated, optionally substituted, hydrocarbon group comprising from 1 to 10 carbon atoms; R.sup.1 representing COOH or SO.sub.3H; wherein one and only one of X.sup.1, X.sup.2, X.sup.4, X.sup.5, X.sup.6, X.sup.7 and X.sup.8 is OH, and wherein one and only one of X.sup.1, X.sup.2, X.sup.4, X.sup.5, X.sup.6, X.sup.7 and X.sup.8 is —O-A-R.sup.1.

2. The aqueous electrolyte according to claim 1, wherein the compound of formula (I) is selected from the group consisting of ##STR00011## wherein: if X=OH, X′=—O-A-R.sup.1, and if X=—O-A-R.sup.1, X′=OH.

3. The aqueous electrolyte according to claim 1, wherein the compound of formula (I) is a compound of formula (I-1,4) ##STR00012## wherein X=—O-A-R.sup.1 and X′=OH.

4. The aqueous electrolyte according to claim 1, wherein A represents (CH.sub.2).sub.n, optionally substituted, wherein n is an integer selected from 1 to 10.

5. The aqueous electrolyte according to claim 1, wherein R.sup.1 is selected from the group consisting of CO.sub.2H, CO.sub.2.sup.−M.sup.+, SO.sub.3H and S.sub.3.sup.−M.sup.+, M.sup.+being selected from the group consisting of Li.sup.+, Na.sup.+, K.sup.+ and NH.sub.4.sup.+.

6. The aqueous electrolyte according to claim 1, wherein A-R.sup.1 is selected from the group consisting of —(CH.sub.2).sub.3—COOH,—(CH.sub.2).sub.4—COOH, —(CH.sub.2).sub.3—SO.sub.3H,—(CH.sub.2).sub.4—SO.sub.3H, —(CH.sub.2).sub.3—SO.sub.3.sup.−+Na and —(CH.sub.2).sub.4—SO.sub.3.sup.−+Na.

7. The aqueous electrolyte according to claim 1, wherein the compound of formula (I) is selected from the group consisting of ##STR00013##

8. The aqueous electrolyte according to claim 1, wherein said electrolyte comprises at least one base.

9. The aqueous electrolyte according to claim 8, wherein the base comprises a hydroxide ion.

10. The aqueous electrolyte according to claim 8, wherein the base is at a concentration of 0.1 to 2 mol/L.

11. The aqueous electrolyte according to claim 1, wherein said electrolyte presents a pH superior or equal to 7 and inferior or equal to 13.5.

12. (canceled)

13. A redox flow battery comprising: −a negative pole comprising an aqueous electrolyte according claim 1, and −a positive pole comprising a positive aqueous electrolyte.

14. A method for generating electricity by at least one redox flow battery, wherein the redox flow battery is defined according to claim 13.

15. The method according to claim 14, wherein said aqueous electrolyte and said positive aqueous electrolyte are pumped at a flow rate comprised between 0.1 and 1.3 mL/min/cm.sup.2.

16. The aqueous electrolyte according to claim 1, wherein A represents (CH2)n, optionally substituted, wherein n is an integer selected from 2 to 5.

17. The aqueous electrolyte according to claim 1, wherein A represents (CH2)n, optionally substituted, wherein n is an integer selected from 3 to 4.

18. The aqueous electrolyte according to claim 1, wherein R1 is selected from the group consisting of CO2H, CO2-M+, SO3H and SO3-M+, and wherein M+is Na+.

19. The aqueous electrolyte according to claim 7, wherein the compound of formula (I) is a compound of formula (M3CH).

20. The aqueous electrolyte according to claim 8, wherein the base is selected from the group consisting of potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, magnesium hydroxide, calcium hydroxide and any combination thereof.

21. The aqueous electrolyte according to claim 8, wherein the base is at a concentration of 0.3 to 1.5 mol/L.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0107] FIG. 1 is a cyclic voltammetry curve (3rd cycle) of compounds of formula (I) recorded at a scan rate of 100 mV.s.sup.−1 and buffered at pH 13 (KOH 10.sup.−1M).

[0108] FIG. 2 is a cyclic voltammetry curve (3rd cycle) of compounds of formula (I) recorded at a scan rate of 100 mV.s.sup.−1 and buffered at pH 14 (KOH 1M).

[0109] FIG. 3 is NMR .sup.1H spectra of a solution at pH 13.9 comprising M3CH compound at 0.05 M concentration obtained from sample at a) t0 and b) t+1month.

[0110] FIG. 4 is NMR .sup.1H spectra of a solution at pH 13.5 comprising M3CH compound at 0.4 M concentration obtained from sample at a) t1 and b) t+1month.

[0111] FIG. 5 is a graph representing the capacity utilization, coulombic and energy efficiencies of a cell test involving a negolyte with compound D4CH

[0112] FIG. 6 is a graph representing two cycles of a cell test involving a negolyte with compound D4SH.

[0113] FIG. 7 is a graph representing the capacity utilization, coulombic and energy efficiencies of a cell test involving a negolyte with compound M4SH.

[0114] FIG. 8 is a graph representing the capacity utilization, coulombic and energy efficiencies of a cell test involving a negolyte with compound M3CH.

[0115] FIG. 9 is a graph representing the capacity utilization and energy density exhibited by a cell test using a negolyte containing compound M3CH.

[0116] FIG. 10 is a graph representing the cell voltage versus time of a typical galvanostatic cycle with 24 hours of rest after full charge along with (insert) the full cycling test involving 7 cycles and 7 rest steps.

[0117] FIG. 11 is a graph representing the cell voltage versus charge and discharge capacities of 7 cycles involving galvanostatic charge +24 hours of rest and galvanostatic discharge.

[0118] FIG. 12 is a graph representing the second cycle performed in constant power cycling mode (1W) with a CV step at the end of charge (limited to 0.25 W) of a cell test involving a negolyte with compound M3CH.

[0119] FIG. 13 is a graph representing the capacity utilization, coulombic and energy efficiencies of a cell test involving a negolyte with compound M3CH and (insert) plotting of the cell voltage as a function of cycling time.

[0120] FIG. 14 is a graph representing the cell voltage versus charge recorded for 30 cycles performed in constant power cycling mode of a cell test involving a negolyte with compound M3CH.

[0121] FIG. 15 is a graph representing the polarization curve realized at 50% SOC using a ramp of +100 A/min and −100 A/min of a cell test involving a negolyte with compound M3CH.

[0122] FIG. 16 is a graph representing the energy density of a battery comprising ARS, AQ-2,7-DS, Complexone or compound M3CH as negolyte, as a function of cycle number.

[0123] FIG. 17 is a graph representing the energy density of a battery comprising ARS, AQ-2,7-DS, Complexone or compound M3CH as negolyte, as a function of the days of constant cycling.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

EXAMPLES

Example 1: Synthesis of Compounds of Formula (I)

[0124] The synthesized Compounds of Formula (I) are listed in Table 1 below.

TABLE-US-00001 TABLE 1 Substitution of the synthesized compounds of formula (I) (I) [00008] Compound (I) X.sup.1 X.sup.4 X.sup.2, X.sup.5, X.sup.6, X.sup.7, X.sup.8 M3CH O—CH.sub.2—CH.sub.2—CH.sub.2—COOH OH H M3SH O—CH.sub.2—CH.sub.2—CH.sub.2—SO.sub.3H OH H M3SNa O—CH.sub.2—CH.sub.2—CH.sub.2—SO.sub.3Na OH H M4SH O—CH.sub.2—CH.sub.2—CH.sub.2—CH.sub.2—SO.sub.3H OH H M4SNa O—CH.sub.2—CH.sub.2—CH.sub.2—CH.sub.2—SO.sub.3Na OH H D3CH O—CH.sub.2—CH.sub.2—CH.sub.2—COOH O—CH.sub.2—CH.sub.2—CH.sub.2—COOH H (comparative) D4CH O—CH.sub.2—CH.sub.2—CH.sub.2—CH.sub.2—COOH O—CH.sub.2—CH.sub.2—CH.sub.2—CH.sub.2—COOH H (comparative) D3SH O—CH.sub.2—CH.sub.2—CH.sub.2—SO.sub.3H O—CH.sub.2—CH.sub.2—CH.sub.2—SO.sub.3H H (comparative) D3SNa O—CH.sub.2—CH.sub.2—CH.sub.2—SO.sub.3Na O—CH.sub.2—CH.sub.2—CH.sub.2—SO.sub.3Na H (comparative) D4SH O CH.sub.2—CH.sub.2—CH.sub.2—CH.sub.2—SO.sub.3H O—CH.sub.2—CH.sub.2—CH.sub.2—CH.sub.2—SO.sub.3H H (comparative)

[0125] These compounds were obtained by the following protocols: [0126] D3CH and D4CH: quinizarin (98%, 0.02 moles) was dissolved in 50 mL of DMF in the presence of ethyl 4-bromobutyrate (95%, 5 eq.) or ethyl 5-bromovalerate and K.sub.2CO.sub.3 (100%, 3 eq.). The mixture was heated at 50° C. for 60 h, which resulted into quantitative product formation with 90% purity by .sup.1H-NMR. Without any further purification, hydrolysis was performed in the presence of 1 M KOH (85%, 3 eq.), 20 mL of ethanol and 20 mL of tetrahydrofurane at room temperature. After reaction finished, reaction mixture was acidified with 1M HCl to pH 2. Product was precipitated as free acid and collected as solid by filtration. [0127] M3CH: quinizarin (98%, 0.02 moles) were dissolved in 50 mL of DMF in the presence of ethyl 4-bromobutyrate (95%, 1 eq.) and K.sub.2CO.sub.3 (100%, 1.1 eq.). The mixture was heated at 50° C. for 48 h. 70% of pure desired product with 30% starting material was obtained. Subsequently, a hydrolysis was performed in the presence of 1 M KOH (85%, 3 eq.), 20 mL of ethanol and 20 mL of tetrahydrofurane at room temperature, followed by a purification through chromatography column. [0128] M3SH and D3SH: quinizarin (98%, 0.01 moles) were dissolved in 50 mL of DMF in the presence of 1,3-propanesultone (98%, 5 eq.) and K.sub.2CO.sub.3 (100%, 5 eq.). The mixture was heated at 70° C. for 48 h. The solution was acidified with 1M HCl to pH 2 and purified by reverse-phase chromatography. [0129] M3SNa, M4SNa and D3SNa: M3SH, M4SH or D3SH, respectively, was treated with NaOH (99%, 1 eq.) in 50 mL of water.

[0130] M4SH and D4SH: quinizarin (98%, 12 mmoles) was dissolved in 50 mL of DMF in the presence of 1,4-butanesultone (98%, 5 eq.) and K.sub.2CO.sub.3 (100%, 5 eq.). The mixture was heated at 70° C. for 48 h. The solution was acidified with 6 M HSO.sub.4 to pH 2 and purified by reverse-phase chromatography.

[0131] These compounds were analyzed by .sup.1H NMR (Table 2): spectra were recorded on BRUKER AC 300 P (300 MHz) spectrometer. Chemical shifts are expressed in parts per million downfield from tetramethylsilane as an internal standard. Data are given in the following order: d value, multiplicity (s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet; br, broad), number of protons, coupling constants J is given in Hertz. Purity is estimated by quantitative-NMR using tetramethylsilane as an internal standard.

TABLE-US-00002 TABLE 2 .sup.1H NMR characterization of compounds of formula (I) Compound of formula (I) .sup.1H NMR (300 MHz, DMSO-d.sub.6) Purity M3CH δ 8.22-8.07 (m, 2H), 7.96-7.80 (m,   96% 2H), 7.61 (d, J = 9.4 Hz, 1H), 7.35 (d, J = 9.4 Hz, 1H), 4.14 (t, J = 6.2 Hz, 2H), 2.57 (t, J = 7.4 Hz, 2H), 2.07-1.92 (m, 2H) M3SH δ 12.86 (s, 1H), 8.19 (td, J = 7.4, 1.7 Hz, 92.7% (suggesting 2H), 8.00-7.82 (m, 2H), 7.66 (d, J = 9.4 the presence of Hz, 1H), 7.40 (d, J = 9.4 Hz, 1H), 4.24 (t, inorganic salts) J = 6.1 Hz, 2H), 2.77 (t, J = 6.6 Hz, 2H), 2.09 (t, J = 7.0 Hz, 2H) M3SNa δ 12.84 (s, 1H), 8.24-8.12 (m, 2H), 7.90 84.9% (impurities (pd, J = 7.3, 1.6 Hz, 2H), 7.63 (d, J = 9.5 of inorganic salts) Hz, 1H), 7.36 (d, J = 9.4 Hz, 1H), 4.23 (t, J = 6.4 Hz, 2H), 2.71 (dd, J = 8.4, 6.5 Hz, 2H), 2.16-2.00 (m, 2H) M4SH δ 12.87 (s, 1H), 8.20 (ddd, J = 10.7, 7.3, 85.4% 2.0 Hz, 2H), 8.00-7.83 (m, 2H), 7.69 (d, J = 9.5 Hz, 1H), 7.40 (d, J = 9.4 Hz, 1H), 4.13 (t, J = 6.0 Hz, 2H), 1.95-1.75 (m, 2H) M4SNa δ 12.83 (s, 1H), 7.58-7.46 (m, 4H), 6.99 80.1% (d, J = 9.6 Hz, 1H), 6.73 (d, J = 9.6 Hz, 1H), 3.78 (t, J = 6.0 Hz, 2H), 3.02 (t, J = 7.5 Hz, 2H), 1.91-1.77 (m, 4H) D3CH δ 12.48 (d, J = 215.4 Hz, 2H), 8.05 (dd, J =  >95% (comparative) 5.8, 3.3 Hz, 2H), 7.82 (dd, J = 5.8, 3.3 Hz, 2H), 7.55 (s, 2H), 2.57 (t, J = 7.4 Hz, 4H), 2.00 (t, J = 6.9 Hz, 4H) D4CH δ 12.03 (s, 2H), 8.03 (dd, J = 5.8, 3.3 Hz,  >95% (comparative) 2H), 7.81 (dd, J = 5.8, 3.3 Hz, 2H), 7.54 (s, 2H), 4.15-4.05 (m, 4H), 2.34 (t, J = 6.8 Hz, 4H), 1.78 (dq, J = 10.7, 4.4, 3.7 Hz, 8H) D3SH δ 8.07 (dd, J = 5.8, 3.3 Hz, 2H), 7.82 (dd, 73.4% (suggesting (comparative) J = 5.8, 3.3 Hz, 2H), 7.55 (s, 2H), 4.19 (t, the presence of J = 6.3 Hz, 4H), 2.78-2.66 (m, 4H), 2.15-2.02 (m, 4H) inorganic salts) D3SNa δ 8.07 (dd, J = 5.8, 3.3 Hz, 2H), 7.81 (dd, 59.4% (impurities (comparative) J = 5.8, 3.3 Hz, 2H), 7.55 (s, 2H), 4.18 (t, of inorganic salts) J = 6.4 Hz, 4H), 2.72-2.65 (m, 4H), 2.07 (p, J = 6.7 Hz, 4H) D4SH δ 8.24 (s, 2H), 8.05 (dd, J = 5.8, 3.3 Hz, 80.8% (comparative) 2H), 7.81 (dd, J = 5.8, 3.3 Hz, 2H), 7.57 (s, 2H), 4.10 (t, J = 5.8 Hz, 4H), 2.56 (d, J = 5.6 Hz, 4H), 1.85 (dp, J = 9.5, 5.3, 4.3 Hz, 8H)

Example 2: Solubility of Compounds of Formula (I)

[0132] The solubility of the compounds of formula (I) and of comparative disubstituted derivatives (D3CH, D4CH, D3SH, D3SNa and D4SH) was evaluated in aqueous solution at various pH by shake-flask method (Table 3). An aqueous solution (containing either KCI 1M, KOH 1M or H.sub.2SO.sub.4 1M) is added over 100 mg of compound by 20 μL portions until complete solubilization. We obtain an approximate range of solubility values calculated as following:

[0133] Smax˜(m/M)/V; m=mass of evaluated compound (g); M=molar mass of evaluated compound (g.Math.mol.sup.−1); V=added volume (L).

TABLE-US-00003 TABLE 3 Solubility of compounds of formula (I) in aqueous solution at various pH Unbuffered Solution Solution solution at pH 14 at pH 0 Compound (I) (KCl 1M) (KOH 1M) (H.sub.2SO.sub.4 1M) Quinizarin 0.00 <0.05 0.00 (comparative) M3CH 0.00 0.53 0.31 M3SH 0.75 0.23 0.31 M3SNa 0.32 0.00 0.46 M4SH 0.51 0.46 Not determined M4SNa 0.65 0.88 0.37 D3CH 0.00 0.42 0.30 (comparative) D3SH 0.69 0.92 0.73 (comparative) D3SNa 0.54 0.44 0.15 (comparative) D4SH 1.58 0.78 0.91 (comparative) D4CH 0.00 0.46 0.00 (comparative)

[0134] These results shows that monosubstituted compounds of formula (I) exhibit a much higher solubility in neutral, basic or acidic media compared to the unsubstituted quinizarin.

[0135] Thus, it would have expected to observe a similar significant difference between the monosubstituted compounds of formula (I) and the comparative disubstituted derivatives.

[0136] Surprisingly, the monosubstituted compounds of formula (I) exhibit a solubility in neutral, basic or acidic media in the same order of magnitude than the corresponding comparative disubstituted derivatives.

[0137] These results demonstrate that the disubstitution of both hydroxyl groups of the quinizarin is not necessary to obtain redox compound having a solubility compatible with their use in an aqueous redox flow battery.

[0138] Without being bound by any particular theory, it seems that the length of A of the O-A-R.sup.1 group has an important role on the solubility of the compound of formula (I).

Example 3: Cyclic Voltammetry Measurements

[0139] Cyclic voltammetry experiments were performed at a 100 mV/s scan rate for compounds M3CH, D3CH, D4CH, M3SH, D3SH, M4SH and D4SH in solution at pH 13(KOH 0.1 M) or pH 14 (KOH 1 M).

[0140] The electrochemical experiments were conducted on an electrochemical working station (BioLogic Science Instruments VSP) at 25° C. using a three-electrodes electrochemical cell, where a Pt wire was employed at the counter electrode (CE), an Ag/AgCl/KCl saturated electrode immerged in a 1 M KOH solution protected from the cell by a porous frit glass served as the reference electrode (RE) and a rotating disc electrode (RDE) mounted with a glassy carbon (GC, 7.069 mm.sup.2) disk was used as the working electrode (WE), respectively. The potential was reported relative to the normal hydrogen electrode (NHE), which was converted from the Ag/AgCl reference electrode (0.230 V versus NHE). The ohmic drop between the WE and RE is determined by current interrupt experiments and leads to a value close to 0.7069 Ω.Math.cm.sup.2. All cyclic voltammetry experiments were conducted by alleviating most of this resistance (85%) using the potentiostat manual ohmic drop compensation. Before each electrochemical measurement, the GC disk electrode was polished using SiC P4000 foil.

[0141] Each recorded cyclic voltammetry of the reduction and the oxidation process of a compound at a given scan rate is analyzed by measuring i.sub.p,a=anodic peak current; i.sub.p,c=cathodic peak current; v=scan rate; E.sub.p,a=anodic peak potential; E.sub.p,c=cathodic peak potential; ΔE.sub.p=E.sub.p,a−E.sub.p,c; the apparent standard redox potential E.sup.0′=(E.sub.p,a−E.sub.p,c)/2.

[0142] Linear sweep voltammetry (LSV) using the RDE at various rotation speed (400 up to 1 000 RPM) were performed to determine the averaged half-wave potential E.sub.1/2.

[0143] The oxidation (D.sub.O) and the reduction (D.sub.R) diffusion coefficients were calculated using Randles-Sevcik (RS) equation i.sub.p=0.4463.Math.n.sup.3/2.Math.F.sup.3/2.Math.A.Math.C.Math.v.sup.1/2.Math.D.sup.1/2.Math.R.sup.−1/2.Math.T.sup.−1/2=Cye.Math.v.sup.1/2.Math.D.sup.1/2,n=number of electrons exchanged during the redox process; F=faradaic number=96485 C.Math.mol.sup.−1; A=electrode active surface; C=redox active molecule concentration; R=gas constant=8.314 J.K.sup.−1.Math.mol.sup.−1; T=bulk temperature=299 K. The experiments are conducted by cyclic voltammetry at various scan rates ranging from 10 mV/s up to 20 V/s.

[0144] A graphic of li.sub.p,al and li.sub.p,cl=f(Cte×v.sup.1/2) is plotted, if the redox process is reversible and diffusion controlled, the peak current should be proportional to the square root of the scan rate. The diffusion coefficients (oxidation and reduction) are then calculated by taking the square of the regression lines slopes. Diffusion coefficients (oxidation and reduction processes) are evaluated by plotting the peak current versus a constant multiplied by the square root of the scan rate. The plots regression line gives a straight line with perfect correlation coefficient (100%) confirming that the redox process is reversible and diffusion controlled. The square of each slope gives the associated coefficient diffusion in cm.sup.2 s.sup.−1.

[0145] The apparent heterogeneous rate constant during oxidation (k.sup.0′.sub.O) /and reduction (k.sup.0′.sub.R) process was calculated using Gileadi's equation (C. Rüssel, W. Jaenicke, Electrochimica Acta, Vol 27, N° 12, 1745-1750, 1982) log k.sup.0′=−0.48α+0.52 +log[(nFαv.sub.cD)/(2.303RT)].sup.1/2; v.sub.c is the critical scan rate, it is calculated by plotting the peak potentials versus the logarithm of the scan rates, and is more precise when a very wide range of scan rates is used, which is the case here (0.010 up to 20 V.s.sup.−1), it is determined at the x-axis of the point of intersection of the regression lines drawn at low and high scan rates; a is the transfer coefficient that is supposed to be close to 0.5 for all presented compounds.

[0146] Peak-to-peak separation ΔEp values were determined from the third cycle of each cyclic voltammogram (FIGS. 1 and 2) and are gathered in the following table 4.

TABLE-US-00004 TABLE 4 Peak-to-peak separation ΔEp of compounds of formula (I) at pH 13 and pH 14 ΔEp (mV) Compound (I) pH 13 pH 14 M3CH 140 31 M3SH 97 40 M4SH 97 39 D3CH (comparative) 267 46 D4CH (comparative) 328 32 D3SH (comparative) 246 40 D4SH (comparative) 390 32

[0147] In the case of comparative disubstituted derivates (D3CH, D4CH, D3SH and D4SH), at pH 13, the electron transfer is relatively slow (240<ΔEp<390mV). On the contrary, monosubstituted compounds of formula (I) according to the invention exhibit a relatively fast electron transfer (in a slightly lower extent for M3CH).

[0148] At pH 14, the measured ΔEp are comprised between 31 and 46 mV for both monosubstituted compounds of formula (I) according to the invention and disubstituted comparatives compounds. These values are close to the theoretical value that is approached when 2 electrons are simultaneously transferred during a fast and reversible redox process (ΔEp=59/2=29.5 mV) and when no protons are exchanged. Either way, the measured ΔEp values at pH 14 indicate that all compounds exhibits an apparent simultaneous 2 electrons transfer during their respective redox process.

[0149] The standard redox process reversibility evaluation is performed in diluted state, at 5 mM of concentration, at pH 14 buffered with 1 M of KOH. Alan J. Bard et al. (A. J. Bard and L. R. Faulkner, Electrochemical Methods, Wiley, N.Y., 2nd edition, 2001) presents the 5 criteria defining the reversibility of a redox process in the handbook of electrochemical methods:

[0150] i) the peak current absolute values must be proportional to the square root of the scan rate;

[0151] ii) the peak potentials must be independent at all scan rates;

[0152] iii) the potential peak difference must be equal to 59/n if no protons are involved, n=number of electron involved in the redox process (2 electrons in this case);

[0153] iv) the ratio of peak current absolute values must be equal to the unity;

[0154] v) the apparent standard redox potential (E.sup.0 ′) must be equal to the half-wave potential (E.sub.1/2).

[0155] Main electrochemical properties of compound of formula (I) are gathered in table 5.

TABLE-US-00005 TABLE 5 Electrochemical parameters of compounds of formula (I) E.sup.0′ E.sub.1/2 D.sub.O × 10.sup.−6 k.sup.0′.sub.O × 10.sup.−2 Compound (I) (V vs NHE) (V vs NHE) (cm.sup.2/s) (cm/s) M3CH −0.484 −0.484 5.2 2.3 M3SH −0.489 −0.489 4.6 3.1 M4SH −0.494 −0.494 5.8 3.1

[0156] Most redox potentials of compound of formula (I) are similar, close to−0.49 V vs NHE which allows to reach an open-circuit-voltage (ocv) of about 1 V at 50% state-of-charge (SOC) in a cell involving standard ferricyanide/ferrocyanide redox couple (E°′=0.5 V vs NHE) in the posolyte.

[0157] The redox process is fast and reversible for a compound of formula (I). This result is important as it discloses the ability of the redox active material to undergo multiple charge and discharge processes without changes of electrochemical properties and performances.

[0158] The diffusion coefficients values vary from 4.5 to 6×10.sup.−6 cm.sup.2/s which is typical of redox active materials used in aqueous redox flow battery (ARFB) negolytes in aqueous medium (see table 6 below). Inversely, the electron transfer kinetics (O stands for oxidant) obtained with compounds of formula (I) (>10.sup.−2 cm/s) are faster than most redox active materials used in ARFB negolytes.

TABLE-US-00006 TABLE 6 Diffusion coefficients and electron transfer kinetics of various comparative redox-active molecules used in negolytes in aqueous redox flow battery Comparative redox active D.sub.O × 10.sup.−6 k.sup.0′.sub.O × 10.sup.−2 material in negolytes (cm.sup.2/s) (cm/s) DHBQ 3.66 0.21 DHAQ 4.8 0.70 DBEAQ 1.58 0.70 DPPEAQ 1.37 Flavine FMN-Na 1.3 0.53 AQ-2,7-DS 3.8 0.72 BTMAP-Vi 3.3 2.2 V.sup.3+/V.sup.2+ 4 0.0017

Example 4: Degradation Rates

[0159] A preliminary degradation study has been performed on M3CH compound at oxidized state in order to exhibit its stability towards two different ionic environments.

[0160] This study consists of NMR .sup.1H measurements of an electrolyte heated at 40° C. and kept under stirring at 300 RPM using a magnetic stirrer.

4.1. High pH and Low Concentration

[0161] The compound was formulated with 0.05 M concentration of M3CH compound, 0.6 M KOH and 0.3 M NaOH which exhibited a pH of 13.9.

[0162] The first NMR .sup.1H spectra (FIG. 3-a) exhibited a typical M3CH proton signature (aromatic protons in the 6.5 to 8.0 ppm region and 3 alkene groups at 1.9; 2.2 and 3.8 ppm) while FIG. 3-b revealed a structural modification through the apparition of 3 distinct proton peak groups (most likely alkenes) at 1.6; 2.1 and 3.4 ppm. This signal modification suggests a deprotection of the alkyle-carboxylic arm, forming the 1,4-dihydroxyanthraquinone back along with its deprotected arm, namely the 3-hydroxy-propionic acid under potassium or sodium salt. Such behavior was detailed in the literature (WO 2019/157437) and is characteristic of a nucleophilic attack i.e. of OH—in strong alkaline environment causing the functionalized arm to be cleaved. An integration of the shifted alkene groups allowed a quantification of the degradation product formation (Table 7) and suggests a degradation rate of roughly 15% per month, which is far from the battery stability requirements.

TABLE-US-00007 TABLE 7 Percentage of degradation product formed over time Time % of degradation (days) product 0 0 31 14-16

[0163] This degradation rate is likely to be enhanced in higher solute concentration (statistically favorable and increased intermolecular collisions number), at higher temperature (thermodynamic activation) and in stronger alkaline solutions (increased OH—concentration).

4.2 Lower pH and Higher Concentration

[0164] In the scope of formulating an electrolyte with decent redox active molecule concentration and exhibiting a sufficient stability, a solution with M3CH compound at 0.4 M concentration at pH 13.5 containing 0.8 M KOH and 0.3 M NaOH was tested following the same procedure as the previous example.

[0165] A similar NMR .sup.1H spectra was recorded the first day (FIG. 4-a) and a month later (FIG. 4-b), showing that the M3CH compound did not undergo any degradation.

[0166] This result suggests that the compounds described in this invention should be used in flow batteries in a pH≤13.5 to make sure that they undergo a minimal amount of degradation throughout cycling.

Example 5: Cycling Tests of Cells Comprising Compound of Formula (I) in Galvanostatic Mode

[0167] The electrochemical diagnosis of the compounds of formula (I) and of the comparative disubstituted compounds that was performed in diluted state in a standard three-electrode electrochemical cell was followed by an evaluation in concentrated state ≥0.2 M) where most secondary reactions linked to the redox active degradation are likely to occur.

[0168] General procedure: Cell tests were carried out on a BCS-815 battery cycler (Biologic) at room temperature. The redox flow battery cell was composed of an Aquivion® membrane (E98-09S Solvay) with an 80 μm thickness serving as separator sandwiched between two GFD porous graphite felts (SGL Carbon group, GFD 4.6 EA), 4.6 mm thick with an active area of 5 or 25 cm.sup.2. The electrodes were inserted into 3 mm PVC frames surrounded by EPDM gaskets. The current collectors were made of graphite composite material provided by SGL and the assembly was compressed by two PVC end-plates. The electrolytes were pumped within the cells through remote-control diaphragm liquid dosing pumps (KNF) at a flow rate of 50 mL/min. The tanks were made of polyethylene connected to polyurethane tubing (4 mm inner diameter). Before each test, the cell materials (membrane and electrodes) were carefully rinsed by using 100 mL of distilled water in each tank that circulates into the cell for one hour. The cell, the process and the tanks were air purged and another rinsing step were performed for one hour before air-purging the whole system. The negolyte, which charged (reduced) form is sensitive to oxygen, was protected by an argon blanket atmosphere by bubbling the gas directly into the negolyte that was kept under circulation for 10 minutes.

[0169] Capacity utilization was calculated by determining the ratio of the discharge capacity to the theoretical capacity available in the electrolytes. Coulombic efficiency was calculated by determining the ratio of the discharge capacity to the charge capacity. Energy efficiency was calculated by determining the ratio of the discharge energy to the charge energy. The energy density was calculated by determining the ratio of the discharge energy to the total volume of posolyte (positive electrolyte) and negolyte (negative electrolyte).

[0170] Under galvanostatic mode, the standard operating current density used was 40 mA/cm.sup.2.

5.1. Cell Comprising Compound D4CH (Comparative)

[0171] Test parameters: [0172] Active area: 5 cm.sup.2 [0173] Negative pole: 10 mL of negolyte comprising 0.2 M of D4CH and 1 M of KOH [0174] Positive pole: 15 mL of posolyte comprising 0.5 M potassium ferrocyanide and 0.1 M KOH [0175] Averaged pH: 13.5 [0176] Cycling test: galvanostatic mode, current of 0.2 A, 1,000 cycles over 2 months of cycling operation [0177] Voltage limits: between 0.55 and 1.35 V.

[0178] FIG. 5 shows the first one hundred cycles recorded.

[0179] An important available capacity (capacity utilization) of 91% was reached (theoretical capacity=107 mAh) whereas very high capacity retention was achieved, reaching 99.995% per cycle (4,000 cycles before losing 20% of initial capacity). The energy efficiency recorded stayed constant at 70% whereas the averaged coulombic efficiency of 99.5% signified that a small proportion of unwanted secondary reactions occurred during the test.

[0180] Such low energy efficiency is recorded throughout the cycling test. This parameter is directly correlated to the overall cell resistance which has a direct influence on the charge and discharge voltage deviation during the cycling operation. The cell resistance includes multifactorial contributions (Arenas et al. Journal of Energy Storage 11 (2017), pp. 119-153.), from namely i) reaction kinetics i.e. when at least one redox couple exhibits low electron transfer kinetics; ii) the membrane through ionic transfer limitations with low cations diffusion coefficients across the membrane (increases with the membrane thickness) i.e. K.sup.+has a lower one compared to Na.sup.+one across Nafion-type membrane; iii) the porous electrode; iv) mass transport limitation i.e. at low electrolyte flow rate; v) electrical contacts coming from i.e. a poor cell design with solid/solid ohmic losses and/or improper voltage terminal connections.

[0181] All parameters are almost equal for each described cell tests of this invention apart from the reaction kinetics which are lower for disubstituted compounds compared to monosubstituted ones at pH lower than 14 (see cyclic voltammetry at pH 13 and pH 14 (FIGS. 2 and 3), which is the case here. This result suggests that, in a stable environment, namely at a pH lower than 13.5, DxCx compounds exhibit low charge-transfer kinetics that decrease the energy efficiency of the cycling operation.

[0182] After this first cycling step of 100 cycles, some water-osmosis phenomenon occurred and prevented an optimal electrolyte circulation to be maintained, highlighting at the same time the difficulty to perform flow battery tests with low electrolyte volumes. Therefore, the cycling performances decreased, nevertheless a total of 1,000 cycles over 2 months were still able to be achieved.

[0183] Post-cycling analyses were carried out using .sup.1H NMR spectroscopy electrolytes. No traces of compound D4CH degradation were visible in the negolyte analysis, showing that this compound exhibited very high chemical stability under cycling. Furthermore, the posolyte analysis showed no trace of anthraquinone moiety, unraveling the very slow diffusion coefficient of compound D4CH across Nafion-type membranes, and by extension of the other presented derivatives. Taking into account the electrolyte-membrane contact time during this cycling test and the NMR spectroscopy resolution, the permeability coefficient of compound D4CH can be estimated below 10.sup.−12 cm.sup.2/s or less than 1% capacity loss per year of electrolyte-membrane contact.

5.2. Cell Comprising Compound D4SH

[0184] Test parameters: [0185] Active area: 5 cm.sup.2 [0186] Negative pole: 9.5 mL of negolyte comprising 0.2 M of D4SH and 1 M of KOH [0187] Positive pole: 15 mL of posolyte comprising 0.5 M potassium ferrocyanide and 0.1 M KOH [0188] Averaged pH: 13.5 [0189] Cycling test: galvanostatic mode, current of 0.1 A, 2 cycles. [0190] Voltage limits: between 0.65 and 1.28 V.

[0191] FIG. 6 shows the two recorded cycles.

[0192] The first charge allowed to reach only 34% of the available capacity (theoretical capacity=102 mAh) of which only 3.6 mAh were discharged (10% of the charged capacity). The second cycle did not exhibit much charged capacity (4.4 mAh).

[0193] The cycling test was stopped and the cell was opened. The analysis of the cell components disclosed the presence of organic materials that was clogging the negolyte electrode at the electrolyte inlet spot. This experimental result suggested that the solubility of D4SH compound was too low at charged state, and such property is not compatible with RFBs requirements.

5.3. Cell Comprising Compound M4SH

[0194] Test parameters: [0195] Active area: 5 cm.sup.2 [0196] Negative pole: 10 mL of negolyte comprising 0.2 M of M4SH and 1 M of KOH [0197] Positive pole: 15 mL of posolyte comprising 0.4 M potassium ferrocyanide and 0.1 M KOH [0198] Averaged pH: 13.5 [0199] Cycling test: galvanostatic mode, current of 0.2 A, 1,000 cycles over 2 months of cycling operation [0200] Voltage limits: between 0.65 and 1.28 V.

[0201] FIG. 7 shows the first one hundred cycles recorded.

[0202] A close to the theory (98%) available capacity was reached (theoretical capacity=107 mAh) whereas very high capacity retention was achieved, reaching 99.999% per cycle (20,000 cycles before losing 20% of initial capacity). The energy efficiency recorded stayed constant at 76% whereas the averaged coulombic efficiency of 99.9% signified that a very low proportion of unwanted secondary reactions occurred during the test.

[0203] After this first cycling step of 100 cycles, some water-osmosis phenomenon occurred and prevented an optimal electrolyte circulation to be maintained, highlighting at the same time the difficulty to perform flow battery tests with low electrolyte volumes. Therefore, the cycling performances decreased, nevertheless a total of 1,000 cycles over 2 months were still able to be achieved.

[0204] Post-cycling analyses were carried out using .sup.1H NMR spectroscopy electrolytes. In addition, no traces of compound M4SH degradation were visible, showing that this compound exhibited very high chemical stability under cycling. Furthermore, the posolyte analysis showed no trace of anthraquinone moiety, unraveling the very slow diffusion coefficient of compound M4SH across Nafion-type membranes, and by extension of the other presented derivatives. Taking into account the electrolyte-membrane contact time during this cycling test and the NMR spectroscopy resolution, the permeability coefficient of compound M4SH can be estimated below 10.sup.−12 cm.sup.2/s or less than 1% capacity loss per year of electrolyte-membrane contact.

5.4. Cell Comprising Compound M3CH

[0205] a) Test 1

Test parameters [0206] Active area: 25 cm.sup.2 [0207] Negative pole: 30 mL of negolyte comprising 0.5 M of M3CH, 0.6 M of KOH, 0.3 M NaOH and 0.8 M KCI [0208] Positive pole: 40 mL of posolyte comprising 0.6 M potassium ferrocyanide and 0.3 M NaOH [0209] Averaged pH: 13.0 [0210] Cycling test: galvanostatic mode, current of 1 A, 85 cycles over 2 months of cycling operation [0211] Voltage limits: between 0.5 and 1.30 V.

[0212] FIG. 8 shows the 85 cycles recorded.

[0213] A high available capacity of 96% was reached (theoretical capacity=804 mAh). It is to be noted that a concentration of 0.5 M (1 M electron) of compound M3CH was used in the negolyte for this cycling test despite the fact that a maximum of 0.53 M of concentration was evaluated at pH 14 for this compound. The available capacity and the energy density reached during this test (close to 10 Wh/L) show that compound M3CH is soluble at every state-of-charge (FIG. 9). Furthermore, a very high capacity retention was achieved, reaching 99.99945% per cycle (36,363 cycles before losing 20% of initial capacity). The energy efficiency recorded stayed constant at 78% whereas the averaged coulombic efficiency of 99.8% signified that a very low proportion of unwanted secondary reactions occurred during the cycling operation. [0214] b) Test 2
Test parameters: [0215] Active area: 25 cm.sup.2 [0216] Negative pole: 60 mL of negolyte comprising 0.5 M of compound M3CH, 0.6 M of KOH, 0.3 M NaOH and 0.4 M KCI [0217] Positive pole: 110 mL of posolyte comprising 0.6 M potassium ferrocyanide and 0.3 M NaOH [0218] Averaged pH: 13.0 [0219] Cycling test: galvanostatic mode, current of 1 A [0220] Voltage limits: between 0.6 and 1.35 V.

[0221] At the end of charge, a rest of 24 hours at ocv was added before each discharge, allowing to quantify the self-discharge of this system in conditions close to its future application. The cycling test was performed during 7 cycles.

[0222] The charge and discharge capacities were plotted in FIG. 10. A high available capacity of 92% (1.13 hours of storage) was reached (theoretical capacity=1,608 mAh). Coulombic efficiencies (CE) after 7 cycles and 1 day of rest after each full charge varied from 99.67 up to 99.83% with an average of 99.76%, compared to the average CE of 99.95% during constant cycling. The self-discharge is thus estimated to be close to 0.19% per storage day, which is a semi-decade lower than the expected limit 1% per day). Furthermore, a very high capacity retention was achieved (FIG. 11), reaching>99.9999% per cycle (200,000 cycles before losing 20% of initial capacity). The energy efficiency recorded stayed at 79%, which is close to the required level of 80% for full-size system.

Example 6: Cycling Tests of Cells Comprising Compound of Formula (I) in Constant Power Cycling Mode

[0223] The standard flow rate of 2 mL/min/cm.sup.2 (50 mL/min for a 25 cm.sup.2 active area) used in most of the cell tests presented above is of the same order of magnitude as those used in the literature (from 4 to 12 mL/min/cm.sup.2). This important flow rate allows limiting and neglecting mass transport losses in the end of charge and discharge, assuring that most of the capacity available in the electrolytes is available. This cycling procedure over a wide range of state-of-charge (typically between 2% and 98%) is not consistent with system conditions, as pumps power must be optimized in order to maximize the overall system yield.

[0224] In addition, galvanostatic mode is not used in RFB system, constant power cycling mode is more realistic to use when making estimations for systems with switch-mode power supplies.

[0225] In the purpose of getting closer to real system conditions, another cell test was performed in constant power cycling mode and the electrolytes were pumped inside the cell at a flow rate of 0.5 mL/min/cm.sup.2 (12 mL/min). A lower flow rate combined with a discharge in constant power cycling mode will necessarily imply a capacity loss due to mass-transport limitations.

[0226] This cell test was performed using materials described above and with the following parameters: [0227] Active area: 25 cm.sup.2 [0228] Negative pole: 370 mL of negolyte comprising 0.3 M of compound M3CH, 0.6 M of KOH and 0.3 M NaOH [0229] Positive pole: 488 mL of posolyte comprising 0.5 M potassium ferrocyanide and 0.3 M NaOH [0230] Averaged pH: 13.5 [0231] Cycling test: constant power cycling mode, power of 1 W [0232] Voltage limits: between 0.7 and 1.25 V.

[0233] At the end of charge, a CV step was performed at 1.25 V with until 0.25 W limit is reached. Such electrolyte volume represents a storage capacity of 4 hours (FIG. 12), it is to be noted that such storage capacities have never been demonstrated to date in the AORFB field.

[0234] The cycling test was performed during 30 cycles over 14 days of cycling operation (FIG. 13).

[0235] As stated before, a lower available capacity was reached (74%) due to mass transport limitations (theoretical capacity=5.95 Ah) whereas very high capacity retention was achieved (FIG. 14), reaching 99.99923% per cycle. Before losing 20% of initial capacity, such battery, after extrapolation, could perform 25 974 cycles or 32.3 years with an average of 2.1 cycles per day, which is, again, an unprecedented performance.

[0236] Such achievement shows that using compounds of formula (I) allows obtaining an AORFB that does not suffer from electrolyte degradation nor cross-over problematics. Hence, it can be envisaged that very few, if not none electrolyte replacement will be needed during all the battery operation (expected to last up to 20 years to justify its investment and utilization).

[0237] The energy efficiency recorded stayed constant at 78% whereas the averaged coulombic efficiency of 99.1% signified that a low proportion of unwanted secondary reactions occurred during the test. Furthermore, at 50% SOC, where the system does not suffer from charge-transfer or mass-transport limitations, a polarization curve was performed in charge and discharge using a ramp of 100 A/min and −100 A/min in order to evaluate the active surface resistance of the cell (FIG. 15).

[0238] A value of 20Ω.Math.cm.sup.2 was obtained which is consistent with an electrochemical cell resistance comprising a Nafion-type membrane with a thickness of 80 μm which diffuses a majority of potassium cations (alkaline medium).

[0239] In addition, a power density of 70 mW.Math.cm.sup.2 was reached in discharge and a power density of 90 mW.Math.cm.sup.2 in charge, showing that higher nominal power densities could be used with such systems.

CONCLUSIVE REMARKS

[0240] The above results support that the technical effect provided by compound of formula (I) of the present invention was surprising and not obvious for a skilled person in the art.

[0241] Indeed, in prior art, redox anthraquinones are usually tested in symmetrical batteries (same electrolyte on each side, it is not a battery strictly speaking), which allows avoiding osmosis, electrolysis or electroosmosis issues. Then, redox anthraquinones are usually tested at a very high flow rate (around 12 mL/min/cm.sup.2, for instance, versus lower than 1.3 in a real battery system), which allows optimizing the performances of the battery while hidding the solubility issues of the anthraquinone at different state of charge. Also, redox anthraquinones are usually tested in galvanostatic cycling (versus a constant power cycling in a real battery system) during low storage duration (<30 min). In addition, an excess of posolyte (in quantity of material and volume) is often used to optimize the performance of the negolyte (the degradation of the negolyte can be hidden by the excess posolyte if this degradation implies the formation of an electroactive species that can be charged and discharged in the same cycling potential window) and to optimize the performance of the battery in general by hiding unwanted secondary reactions such as electrolysis and air leak at the negative pole; ferricyanide and ferrocyanide cross-over from the positive to the negative pole.

[0242] On the contrary, according to the present invention, under near-real conditions (low flow rate, storage of 4 hours of energy, constant power cycling mode) and at pH 13.5, runs a redox flow battery with a degradation of 0.62% capacity per year (5 times more stable than values of prior art despite much more drastic conditions and more in line with the actual application).

[0243] In addition, the present invention provides an energy density close to 10 Wh/L (3 times higher than values of prior art).

Example 7: Cycling Tests of Cells Implementing Compounds of the Prior Art in Constant Power Cycling Mode

[0244] Compounds ARS, AQ-2,7-DS and Complexone were tested as negolyte under near-actual operating conditions, i.e.: [0245] Molar excess equivalents of the non-limiting side=10%. [0246] Charge and discharge in constant power cycling mode. Constant cycling mode. No CV step at the end of the discharge.

[0247] Also, the effect of volume/storage duration on performances are disclosed. The higher the volume, the longer the storage duration.

[0248] Moreover, the effect of flowrate on performances are disclosed. System conditions impose a flowrate below 1 mL/min/cm.sup.2.

[0249] These tested compounds were as follows:

##STR00009##

[0250] ARS: 1,2-Dihydroxyanthraquinone-3-sulfonic acid sodium salt (Alizarin Red S).

[0251] AQ-2,7-DS: Anthraquinone-2,7-disulfonic acid disodium salt.

[0252] Complexone: 3,4-Dihydroxyanthraquinon-2-yl-methylimino-diacetic acid.

[0253] To be considered as relevant for industrial applications under operating conditions, the battery comprising each negolyte should simultaneously fulfil the following parameters: [0254] Energy density (considering both electrolytes volumes) under constant power cycling mode≥40 mW/cm.sup.2 must be ≥4 Wh/L [0255] Storage duration (during discharge) under constant power cycling mode ≥40 mW/cm.sup.2 must be ≥3 hours [0256] Stability (days before losing 20% of initial capacity) under constant power cycling mode ≥40 mW/cm.sup.2 must be ≥365 days

[0257] 7.1. Study of ARS compound

[0258] Two different batteries comprising ARS as negolyte were tested under the same cycling parameters described above.

The two batteries have the following parameters: [0259] Active area: 25 cm.sup.2 [0260] Negative pole: 0.2 M of ARS and 2M of KOH [0261] Positive pole: 0.3 M potassium ferrocyanide and 1.4M of KOH [0262] Averaged pH: 14.0 [0263] Cycling test: constant power cycling mode, power of 1 W. At the end of charge, a CV step was implemented at 1.3 V with until 0.25 W limit is reached. [0264] Voltage limits: between 0.7 and 1.3 V.
Battery n°1: [0265] Electrolyte volumes (V): 60 mL of negolyte and 88 mL of posolyte [0266] Flowrate (Q): 5 mL/min/cm.sup.2 (non-limiting, ideal conditions) during 1.9 days of constant cycling and, afterwards the flowrate is decreased down to 0.5 mL/min/cm.sup.2 (limiting, system conditions)
Battery n°2: [0267] Electrolyte volumes (V): 120 mL of negolyte and 176 mL of posolyte [0268] Flowrate (Q): 5 mL/min/cm.sup.2 (non-limiting, ideal conditions) during 3.8 days of constant cycling and, afterwards the flowrate is decreased down to 0.5 mL/in/cm.sup.2 (limiting, system conditions).

[0269] The results of the cycling tests are gathered in the following table 8.

TABLE-US-00008 TABLE 8 Comparison of performances over 30 cycles (c) of batteries 1 and 2 which comprises 60 mL (1.sup.st battery) or 120 mL (2.sup.nd battery) of ARS; each battery was cycled using Battery test number Battery Battery Battery Battery no1 no2 no1 no2 Volume (mL)/Flowrate 60/5 120/5 60/0.5 120/0.5 (mL/min/cm.sup.2) Energy Density after 30 c at 3.2 3.5 2.5 2.2 40 mW/cm.sup.2 (Wh/L) Average CE over 30 c 98.79% 98.48% 98.79% 98.56% (%) Storage duration of the 1st 0.50 1.16 0.41 0.77 cycle at 40 mW/cm.sup.2 (hours) Capacity retention after 30 c 95.27% 89.82% 92.06% 86.22% (%) Capacity retention per cycle 99.84% 99.64% 99.72% 99.51% over 30 c (%/cycle) Stability in cycles 138 62 81 45 (−20%) Capacity retention per day 96.57% 96.68% 93.87% 94.34% over 30 c (%/day) Stability in days 6.4 6.6 3.5 3.8 (−20%)
two different flowrates (5 and 0.5 mL/min/cm.sup.2). The energy density considers both electrolyte volumes; the coulombic efficiency (CE) is averaged over the 30 cycles; the storage duration (discharge process expressed in hours) of the 1st cycle is represented; the capacity retention (%) after 30 cycles is shown; the capacity retention is either expressed by percentage of capacity loss per cycle (%/cycle) either per day of constant cycling (%/day); the stability expressed the extrapolation of the number of cycles or days of constant cycling before losing 20% of initial capacity.

[0270] Using constraints close to real systems, i.e. actual operating conditions (higher storage duration or volume, lower flowrate), the performances of ARS, an anthraquinone derivative which the structure involves a combination of hydroxy and sulfonate groups, are very low in terms of stability (a few days of constant cycling before losing 20% of capacity) and coulombic efficiency (<99%). These results point out that this anthraquinone undergoes degradation throughout cycling. In addition, it can be noticed that the stability depends on the time of cycling and on the flowrate (see stability in days of cycling shown in Table 8) but not on the volume of electrolyte. The degradation rate seems to be lowered (about twice as slow with higher flowrate) when non-limiting flowrate is implemented, suggesting that, for instance, better fluid homogeneity in the electrode lowers the chance of local voltage discrepancies leading to the anthraquinone chemical modification.

[0271] In conclusion, using ARS, under this battery environment and cycling conditions, is not suitable for the application under actual operating conditions. In particular, a battery implementing ARS does not fulfil the fixed key parameters of energy density; storage duration and stability. On the contrary compounds of formula (I) and batteries according to the present invention meet such key parameters of energy density; storage duration and stability simultaneously.

[0272] 7.2. Study of AQ-2, 7-DS compound

[0273] Two different batteries comprising AQ-2,7-DS as negolyte were tested under the same cycling parameters described above.

[0274] The two batteries have the following parameters: [0275] Active area: 25 cm.sup.2 [0276] Negative pole: 0.3 M of AQ-2,7-DS, 0.4M of KCI and 0.1M of KOH [0277] Positive pole: 0.5 M potassium ferrocyanide and 0.1M of KOH [0278] Averaged pH: 13.0 [0279] Cycling test: constant power cycling mode, power of 1 W. At the end of charge, a CV step was performed at 1.0 V with until 0.25 W limit is reached. [0280] Voltage limits: between 0.5 and 1.0 V.
Battery n°3: [0281] Electrolyte volumes (V): 60 mL of negolyte and 79 mL of posolyte [0282] Flowrate (Q): 5 mL/min/cm.sup.2 (non-limiting, ideal conditions) during 1.8 days of constant cycling and, afterwards the flowrate is decreased down to 0.5 mUmin/cm.sup.2 (limiting, system conditions)
Battery n°4: [0283] Electrolyte volumes (V): 120 mL of negolyte and 176 mL of posolyte [0284] Flowrate (Q): 5 mL/min/cm.sup.2 (non-limiting, ideal conditions) during 4.2 days of constant cycling and, afterwards the flowrate is decreased down to 0.5 mUmin/cm.sup.2 (limiting, system conditions).

[0285] The results of the cycling tests are gathered in the following table 9.

TABLE-US-00009 TABLE 9 Comparison of performances over 30 cycles (c) of batteries 3 and 4 which comprises 60 mL (3rd battery) or 120 mL (4th battery) of AQ-2,7-DS; each battery was cycled using two different flowrates (5 and 0.5 mL/min/cm.sup.2). The energy density considers both electrolyte volumes; the coulombic efficiency (CE) is averaged over the 30 cycles; the storage duration (discharge process expressed in hours) of the 1st cycle is represented; the capacity retention (%) after 30 cycles is shown; the capacity retention is either expressed by percentage of capacity loss per cycle (%/cycle) either per day of constant cycling (%/day); the stability expressed the extrapolation of the number of cycles or days of constant cycling before losing 20% of initial capacity. Battery test number Battery Battery Battery Battery no3 no4 no3 no4 Volume (mL)/Flowrate 60/5 120/5 60/0.5 120/0.5 (mL/min/cm.sup.2) Energy Density 4.0 4.1 2.9 0.0 after 30 c at 40 mW/cm.sup.2 (Wh/L) Average CE over 30 c 99.31% 99.31% 99.46% 0.00% (%) Storage duration 0.57 1.19 0.40 0.00 of the 1st cycle at 40 mW/cm.sup.2 (hours) Capacity retention 98.24% 96.19% 98.82% 0.00% after 30 c (%) Capacity retention 99.94% 99.87% 99.96% 0.00% per cycle over 30 c (%/cycle) Stability in cycles 378 173 563 0 (−20%) Capacity retention 98.95% 98.87% 99.18% 0.00% per day over 30 c (%/day) Stability in days 21.1 19.6 27.1 0.0 (−20%)

[0286] The electrolytes have been formulated so as to adapt AQ-2,7-DS to the alkaline medium. Using low constraints (high flowrate, low volume), such anthraquinone derivative which structure involves two sulfonate groups exhibit a good energy density (>4 Wh/L) but the storage duration and the stability remain too low. Using constraints close to real systems (higher storage duration or volume, lower flowrate), the AQ-2,7-DS precipitates directly after decreasing the flowrate down to 0.5 mL/min/cm.sup.2. This brutal result highlights the important impact of the flowrate on the apparent battery performances.

In conclusion, this active material, under this battery environment and cycling conditions, does not fulfil the key requirements for working under actual operating conditions, i.e. the minimum performances in terms of energy density, storage duration and stability detailed in the introductive part of example 7.

[0287] 7.3. Study of Complexone Compound

[0288] A battery comprising Complexone as negolyte were tested under the same cycling parameters described above.

This battery n°5 has the following parameters: [0289] Active area: 25 cm.sup.2 [0290] Negative pole: 40 mL comprising 0.3 M of Complexone and 1M of KOH [0291] Positive pole: 66 mL comprising 0.4 M potassium ferrocyanide and 1M of KOH [0292] Averaged pH: 13.7 [0293] Cycling test: constant power cycling mode, power of 1 W. At the end of charge, a CV step was performed at 1.3 V with until 0.25 W limit is reached. [0294] Voltage limits: between 0.6 and 1.3 V. [0295] Flowrate: 5 mL/min/cm.sup.2 (non-limiting, ideal conditions) during 4.2 days of constant cycling and, afterwards the flowrate is decreased down to 0.5 mL/in/cm.sup.2 (limiting, system conditions).

[0296] The results of the cycling tests are gathered in the following table 10.

TABLE-US-00010 TABLE 10 Comparison of performances over 30 cycles (c) of battery no5 using two different flowrates (5 and 0.5 mL/min/cm.sup.2). The energy density considers both electrolyte volumes; the coulombic efficiency (CE) is averaged over the 30 cycles; the storage duration (discharge process expressed in hours) of the 1st cycle is represented; the capacity retention (%) after 30 cycles is shown; the capacity retention is either expressed by percentage of capacity loss per cycle (%/cycle) either per day of constant cycling (%/day); the stability expressed the extrapolation of the number of cycles or days of constant cycling before losing 20% of initial capacity. Battery test number Battery Battery no5 no5 Volume (mL)/Flowrate (mL/min/cm.sup.2) 40/5 40/0.5 Energy Density after 30 c at 40 mW/cm.sup.2 4.8 4.5 (Wh/L) Average CE over 30 c 98.7% 98.88% (%) Storage duration of the 1st cycle at 40 0.54 0.53 mW/cm.sup.2 (hours) Capacity retention after 30 c 90.79% 89.89% (%) Capacity retention per cycle over 30 c 99.68% 99.65% (%/cycle) Stability in cycles 69 63 (−20%) Capacity retention per day over 30 c 93.72% 93.28% (%/day) Stability in days 3.4 3.2 (−20%)

[0297] Using constraints close to real systems, i.e. actual operating conditions (higher storage duration or volume, lower flowrate), the performances of Complexone, an anthraquinone derivative which structure involves a combination of hydroxy and carboxylic groups attached to a tertiary amine, are good in terms of energy density ≥4.5 Wh/L) but are very low in terms of stability (a few days of constant cycling before losing 20% of capacity) and coulombic efficiency (<99%). These results point out that Complexone undergoes degradation throughout cycling. In addition, it can be noticed that the stability does not depend on the flowrate (see stability in days of cycling shown in Table 10).

[0298] In conclusion, this active material, under this battery environment and cycling conditions, does not fulfil the key requirements for working under actual operating conditions, i.e. the minimum performances in terms of energy density, storage duration and stability detailed in the introductive part of example 7.

[0299] 7.4. Comparison of ARS, AQ-2, 7-DS and Complexone with a Compound of Formula (I) of the Invention (M3CH) [0300] Performances are compared over 5 days of constant cycling, under constant power cycling mode. [0301] ARS battery test, AQ-2,7-DS battery test and Complexone battery test are those described above in examples 7.1, 7.2 and 7.3. [0302] M3CH battery test corresponds to the example n°6 of this application.

[0303] The comparison between these four systems are shown in FIGS. 16 and 17, and in Table 11.

TABLE-US-00011 TABLE 11 Comparison of performances over 5 days of constant cycling of four battery tests which negolyte comprises various active material; each battery used a specific negolyte volume; each battery used a flowrate of 0.5 mL/min/cm.sup.2. The energy density considers both electrolyte volumes; the coulombic efficiency (CE) is averaged over the 30 cycles; the storage duration (discharge process expressed in hours) of the 1st cycle is represented; the capacity retention (%) after 30 cycles is shown; the capacity retention is either expressed by percentage of capacity loss per cycle (%/cycle) either per day of constant cycling (%/day); the stability expressed the extrapolation of the number of cycles or days of constant cycling before losing 20% of initial capacity. Battery test number/Example number Battery Battery Battery no2/ no4/ no5/ Exam- Exam- Exam- Exam- ple 7.1 ple 7.2 ple 7.3 ple 6 Active ARS AQ-2,7-DS Complexone M3CH molecule in the negolyte Volume (mL)/ 120/0.5 120/0.5 40/0.5 370/0.5 Flowrate (mL/min/cm.sup.2) Energy Density 1.9   0.0 3.5 4.6 after 5 days at 40 mW/cm.sup.2 (Wh/L) Average CE 98.64% 0 98.98% 99.18% over 5 days (%) Storage 0.77 0 0.53 4.05 duration of the 1 st cycle at 40 mW/cm.sup.2 (hours) Capacity 72.9686% 0% 71.4600% 99.9898% retention after 5 days (%) Capacity 99.5010% 0% 99.6977% 99.9992% retention per cycle over 5 days (%/cycle) Stability 45 0 74 28449 in cycles (−20%) Capacity 93.8917% 0% 93.5002% 99.9980% retention per day over 5 days (%/day) Stability 3.5   0.0 3.3 10942.1 in days (−20%)

[0304] The comparison of the performances of different anthraquinone derivatives (ARS, AQ-2,7-DS, Complexone and M3CH), having very different water-solubilizing functions in alkaline medium have been performed using the same cycling conditions (the voltage limits have been optimized in each case considering the open-circuit voltage imposed by the studied anthraquinone/ferrocyanide redox couple) and using dedicated formulations.

[0305] The results show that only compounds according to the invention (here as illustrative purpose M3CH) allow obtaining a battery fulfilling the requirements in terms of energy density, storage duration and stability (i.e. an energy density greater than or equal to 4 Wh/L, a storage duration greater than or equal to 3 hours, and a stability greater than or equal to 365 days).

[0306] Thus, it is demonstrated that the anthraquinone compounds of the prior art do not provide sufficient performance under actual operating conditions as active material in the negolyte of an AORFB. On the contrary it has been demonstrated that a compound of formula (I) according to the invention allow operating an aqueous organic redox flow battery featuring very high performances in terms of energy density, storage duration and stability even under actual operating conditions.