Non-aqueous redox flow battery

Abstract

a positive compartment in which the positive electrode is placed and through which a non-aqueous liquid positive electrode electrolyte is flowed; a negative compartment in which the negative electrode is disposed and through which a non-aqueous liquid negative electrode electrolyte is flowed; an ion exchange membrane disposed between the positive compartment and the negative compartment; Equipped with the non-aqueous liquid positive electrolyte comprises a solution of copper triflate or tetrafluoroborate complexes [Cu(I) or Cu(II)] in at least one organic solvent; the non-aqueous liquid negative electrode electrolyte comprises a solution of at least one benzothiadiazole having the general formula (I) in at least one organic solvent; [Formula 1] JPEG2023551447000033.jpg7363 wherein R1 and R2, which may be the same or different, represent a hydrogen atom or a C1-C 20 , preferably C1 to C 10 or represents a —O—R group, where R is a C1-C 20 , preferably C1 to C 10 or R3 is selected from the group consisting of -(CH2) n COOR4 groups, where R4 is C1-C 20 , preferably C1 to C 10 wherein n is an integer of 1 to 10, preferably an integer of 1 to 8, or R3 is -(CH2) n OR group, where R and n have the same meanings as above, or R is -(CHCHO) n R groups, where R and n have the same meanings as above, or R is -(CH) n CN group, n having the same meaning as above, or R3 is -(CH2) n NR4R5 groups, where R4 and n have the same meanings as above, and R5 is selected from C1-C 20 , preferably C1 to C10 or R3 is selected from the group consisting of -(CH2) n R is selected from the group CONR4R5, where R4, R5 and n are saturated or unsaturated and have the same meaning as above, or R3 is -(CH2) n Si(R4)3 group, where R4 and n have the same meaning as above, or R3 is -(CH2) n Si(OR4)3 groups, where R4 and n have the same meaning as above, except that at least one of R1 and R2 is different from hydrogen and at least one of R1 and R2 is in the 2-position of the phenyl. The non-aqueous redox flow batteries (RFBs) may be advantageously used in devices requiring medium to high power (e.g., about 10 kW to 100 MW) for several hours (i.e., more than one hour), such as in industrial plants or devices for storing energy from alternative energy sources (such as solar or wind energy) for subsequent use (e.g., for domestic or industrial, such as consumer or commercial, use) or sale.

Description

Technical Field

[0001] The present invention relates to a non-aqueous redox flow battery (RFB).

[0002] More specifically, the present invention includes a positive compartment where the positive electrode is located and a non-aqueous liquid positive electrode electrolyte flows, a negative compartment where the negative electrode is located and a non-aqueous liquid negative electrode electrolyte flows, and an ion exchange membrane located between the positive compartment and the negative compartment. The non-aqueous liquid positive electrode electrolyte comprises a solution of copper triflate or tetrafluoroborate complex [Cu(I) or Cu(II)] in at least one organic solvent, and the non-aqueous liquid negative electrode electrolyte comprises a solution of at least one benzothiadiazole having a specific general formula (I) provided below in at least one organic solvent. The present invention relates to a non-aqueous redox flow battery (RFB).

[0003] The non-aqueous redox flow battery (RFB) can be advantageously used in devices that require medium to high power (e.g., about 10 kW to 100 MW) for several hours (i.e., more than 1 hour), such as devices for storing energy from industrial plants or alternative energy sources (such as solar energy or wind energy) for subsequent use (e.g., for household, or industrial use such as domestic or commercial) or for sale.

Background Art

[0004] Redox flow batteries (RFBs) are becoming an increasingly promising technology in the field of energy storage due to their flexibility and scalability. However, more importantly, since the storable energy and the supplied power are separated, unlike all other secondary batteries, they have a low impact on the environment and operate safely.

[0005] A redox flow battery (RFB) is a type of rechargeable battery that converts chemical energy directly into electrical energy by flowing an electrolyte containing a solution of one or more electroactive species through an electrochemical cell. The electrochemical cell typically consists of a negative compartment (or negative half-cell) and a positive compartment (or positive half-cell) separated by an ion exchange membrane. By storing these electrolytes in external tanks, the power component (i.e., the output power depending on the dimensions and design of the electrochemical cell) and the energy component (i.e., the stored energy depending on the dimensions of the external tank and the concentration of the electrolyte contained in the external tank) are separated, bringing benefits in terms of flexibility in its application.

[0006] The characteristics of the solution of one or more electroactive species depend on various factors such as, for example, the concentration of the electroactive species reacting in the solution, the number of electrons moving within the negative or positive compartment (or half-cell), and the reaction potential, and they have a high energy density.

[0007] Most redox flow batteries (RFBs) use an aqueous solution of an inorganic electrolyte. Recently, organic electrolytes have also been studied and have proven interesting due to their stability in the redox cycle. This type of redox flow battery (RFB) is based on organic reagents, characterized by high energy density, low environmental impact (not using heavy metals or corrosive solutions), and low cost. In fact, the price of vanadium is very high and is greatly affected by market fluctuations, so using organic reagents can avoid the use of elements whose distribution may be concentrated in a few countries and dominate the market. Furthermore, the aqueous system is limited by the small electrochemical stability window of water (about 1.2V). Therefore, many studies are underway to develop non-aqueous flow batteries with a much wider electrochemical range.

[0008] The fundamental operating characteristics of redox flow batteries (RFBs) depend on both the stability and solubility (>0.5–1M) of the reactive species in the electrolyte. Commonly used solvents are acetonitrile, propylene carbonate, ethylene carbonate, or mixtures thereof. Acetonitrile is the most commonly used in cyclic voltammetry. In fact, although it is flammable and highly volatile, it is a polar solvent capable of dissolving the supporting electrolyte and polar species that may be formed in redox flow batteries (RFBs), and also has a particularly broad electrochemical range (above 5V). Propylene carbonate, ethylene carbonate, or mixtures thereof are of great interest due to their lower flammability.

[0009] Since the first redox flow battery (RFB) using a non-aqueous solvent was reported in Non-Patent Literature 1 by Singh P., many redox pairs have been tried, both with metals [Ru(acac)3,Ru(bpy)3,Fe(ppy)3,V(acac)3,Mn(acac)3] and nonmetals (2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), N-methylphthalimide, quinoxaline, anthraquinone, viologen, benzothiadiazole).

[0010] For example, Patent Document 1, issued on behalf of the present applicant, describes a non-aqueous redox flow battery (RFB), A positive compartment is where the positive electrode is placed and a non-aqueous liquid positive electrode electrolyte flows through it, A negative compartment is located where the negative electrode is positioned and through which a non-aqueous liquid negative electrode electrolyte flows, An ion exchange membrane is placed between the positive and negative compartments, Equipped with, The non-aqueous liquid cathode electrolyte comprises a solution of copper triflate or tetrafluoroborate complex [Cu(I) or Cu(II)] in at least one organic solvent. The non-aqueous liquid negative electrode electrolyte comprises a solution of at least one benzothiadiazole or a derivative thereof in at least one organic solvent. Regarding non-aqueous Redux flow batteries (RFBs).

[0011] Preferably, the non-aqueous liquid anode electrolyte comprises a solution of benzothiadiazole (1). [ka]

[0012] The above-mentioned non-aqueous redox flow batteries (RFBs) are said to be advantageously suited for use in devices requiring medium to high power (e.g., approximately 100 kW to 100 MW) for several hours (i.e., more than one hour), such as industrial plants or devices for storing energy from alternative energy sources (such as solar or wind energy) for subsequent use (e.g., household use) or sale.

[0013] Non-patent document 2 states that the cathode liquid (non-aqueous liquid cathode electrolyte) is a substituted dialkoxybenzene having formula (II), [ka] The anolyte (non-aqueous liquid anode electrolyte) is a benzothiadiazole having formula (III). [ka] Non-aqueous redox flow batteries (RFBs) are described. R4 = H, CN; R5 = H, CH3; CH3O; F R6=H;CH3; R7=H,CN, And, We study their stability and the degradation phenomena that result from oxidation-reduction reactions. However, Zhang J. et al. have reported that even when the most chemically stable anode / cathode pair is present, the lifecycle of such non-aqueous redox flow batteries (RFBs) is largely (but not exclusively) limited by parasitic reactions due to crossover of reaction products between compartments of the non-aqueous redox flow battery (RFB). They also report that in many cases, the cycle performance of these non-aqueous redox flow batteries (RFBs) appears to be strongly influenced by the low selectivity of the membrane.

[0014] In Non-Patent Document 3, Zhao Y. et al. reported using 2,1,3-benzothiadiazole (BzNSN) as a model anode liquid (aqueous liquid anode electrolyte) in a non-aqueous redox flow battery ("RFB") to study the effects of various supporting electrolytes. Zhao Y. et al. observed that changing the components of the supporting electrolyte altered both the redox potential and electrochemical stability of 2,1,3-benzothiadiazole. In particular, as the size of the supporting electrolyte cations increased, the redox potential of 2,1,3-benzothiadiazole became increasingly negative, and Li + -1.63V vs Ag / Ag + From, K + For larger cations such as tetraethylammonium, the vortex is -1.82V vs Ag / Ag + It was observed that this occurred. Furthermore, larger cations increased the electrochemical stability of the model compound.

[0015] Non-patent document 4 states that the cathode liquid (non-aqueous liquid cathode electrolyte) is a substituted dialkoxybenzene having formula (II), [ka] The anolyte (non-aqueous liquid anode electrolyte) is a benzothiadiazole having formula (IV). [ka] Non-aqueous redox flow batteries (RFBs) are described. Here, R=H, CH3, OCH3, F, CF3, and we are studying the stability and degradation phenomena resulting from redox reactions, particularly the lifetime of anionic radicals in acetonitrile. A discrepancy arises between these lifetimes and the stability of redox flow batteries (RFBs), indicating the presence of further parasitic reactions.

[0016] From the above, it can be seen that although benzothiadiazole and its derivatives are effective redox species in non-aqueous redox flow batteries (RFBs), the high reactivity of radicals formed during the charging phase of such non-aqueous redox flow batteries makes the discharge operation difficult. In fact, the formed BTD · Radicals tend to bind to the membrane located between the positive and negative compartments, or to the graphite electrodes present in those compartments, causing parasitic reactions. [Prior art documents] [Patent Documents]

[0017] [Patent Document 1] International Patent Application No. 2018 / 007991 [Non-patent literature]

[0018] [Non-Patent Document 1] Singh P., in “Journal of Power Sources” (1984), Vol. 11, pg. 135-142 [Non-Patent Document 2] Zhang J. et al, “Journal of power sources” (2018), Vol. 397, pg. 214-222 [Non-Patent Document 3] Zhao Y. et al, “Journal of Material Chemistry A” (2020), DOI: 10.1039 / D0TA02214D (“Accepted Manuscript”) [Non-Patent Document 4] Huang J. et al, “Journal of Material Chemistry A” (2018), Vol. 6, pg. 6251-6254 [Overview of the Initiative]

[0019] Therefore, the applicant faced the problem of finding a benzothiadiazole derivative that does not have the above-mentioned drawbacks and can thereby make the non-aqueous redox flow battery (RFB) used in it more stable.

[0020] The applicant claims that certain benzothiadiazole derivatives having the specific general formula (I) shown below have good chemical stability during charge-discharge cycles of non-aqueous redox flow batteries (RFBs) in which they are used, and therefore can make said non-aqueous redox flow batteries (RFBs) more stable. Furthermore, these benzothiadiazole derivatives have very good electrochemical properties as measured by cyclic voltammetry and high solubility in the organic solvents used (particularly acetonitrile and propylene carbonate). In addition, these benzothiadiazole derivatives exhibit good performance, namely high potential difference (E°) and high energy density (ρ°) in open circuits. e It is possible to provide a non-aqueous redox flow battery (RFB) having ).

[0021] Therefore, the object of the present invention is a non-aqueous redox flow battery (RFB), A positive compartment is where the positive electrode is placed and a non-aqueous liquid positive electrode electrolyte flows through it, A negative compartment is located where the negative electrode is positioned and through which a non-aqueous liquid negative electrode electrolyte flows, An ion exchange membrane is placed between the positive and negative compartments, Equipped with, The non-aqueous liquid positive electrolyte comprises a solution of copper triflate or tetrafluoroborate complex [Cu(I) or Cu(II)] in at least one organic solvent. The non-aqueous liquid negative electrolyte comprises a solution of at least one benzothiadiazole having the general formula (I) in at least one organic solvent.

Chemical formula

[0022] In this specification and the appended claims, unless otherwise specified, the definition of a numerical range always includes the values ​​at both ends.

[0023] In this specification and the appended claims, the term “equipped with” also includes the term “substantially consisting of” or “consisting of.”

[0024] In this specification and in the claims, "C1-C 20 The term "alkyl group" refers to a saturated or unsaturated linear or branched alkyl group having 1 to 20 carbon atoms. 20 Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, and n-dodecyl.

[0025] According to a preferred embodiment of the present invention, the copper triflate or tetrafluoroborate complex [Cu(I) or Cu(II)] may be selected from, for example, tetrakisacetonitrile copper(I) triflate [Cu(NCCH3)4·CF3SO3], copper(II) trifluoromethanesulfonate [Cu(CF3SO3)2], tetrakisacetonitrile copper(I) tetrafluoroborate [Cu(NCCH3)4·BF4], or a mixture thereof.

[0026] According to a preferred embodiment of the present invention, the general formula (I) is: R1 and R2, which are either identical or distinct from each other, represent a hydrogen atom or an -OR3 group, where R3 is -(CH2) n COOR4 groups are selected, and R4 is C1~C 20 Preferably C1~C 10 R3 is selected from a linear or branched alkyl group, saturated or unsaturated, where n is an integer consisting of 1 to 10, preferably 1 to 8, or R3 is -(CH2CH2O) n Selected from the R4 group, where R4 and n have the same meanings as above, preferably representing a propyloxycarbonylethyloxy group, a methoxycarbonylethyloxy group, or a methoxyethoxyethyloxy group. However, at least one of R1 and R2 is different from hydrogen, and at least one of R1 and R2 is located at the 2 position of phenyl. Table 1 lists specific examples of compounds having general formula (I) that are useful for the purposes of the present invention.

[0027] [Table 1]

[0028] For the purposes of the present invention, starting with a solution of copper(II) triflate complex [Cu(II)], a solution comprising at least one benzothiadiazole having general formula (I) is supplied to the negative compartment in the reduced form (BTD). ·- It should be noted that it is reduced to obtain benzothiadiazole having general formula (I) in )

[0029] The electrolytes described above may include at least one supporting electrolyte. The supporting electrolyte is capable of maintaining charge equilibrium between the electrolyte in the negative compartment and the electrolyte in the positive compartment, but does not participate in the reaction. Generally, the supporting electrolyte must be chemically inert over the potential range considered, have high ionic conductivity to ensure low resistance to the passage of current, and do not interfere with electron exchange on the electrode surface.

[0030] According to one embodiment of the present invention, the electrolyte comprises at least one supporting electrolyte selected from, for example, lithium tetrafluoroborate (LiBF4), lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), methyltrifluoromethanesulfonate (LiCF3SO3), lithium bis(trifluoromethylsulfonyl)imide [Li(CF3SO2)2N], tetraethylammonium tetrafluoroborate (TEABF4), tetrabutylammonium tetrafluoroborate (TBABF4), or mixtures thereof. Lithium tetrafluoroborate (LiBF4) and tetrabutylammonium tetrafluoroborate (TBABF4) are preferred.

[0031] According to preferred embodiments of the present invention, the organic solvent may be selected from, for example, acetonitrile, dimethylacetamide, diethyl carbonate, dimethyl carbonate, γ-butyrolactone (GBL), propylene carbonate (PC), ethylene carbonate (EC), N-methyl-2-pyrrolidone (NMP), fluoroethylene carbonate, N,N-dimethylacetamide, or mixtures thereof. Acetonitrile and propylene carbonate (PC) are preferred.

[0032] In this invention, it should be noted that it is preferable to use the same solvent in both the positive and negative compartments in order to prevent the problem of possible diffusion through the ion exchange membrane, which would result in the problem of contamination between the two compartments.

[0033] It should also be noted that both the copper triflate or tetrafluoroborate complex [Cu(I) or Cu(II)] and the benzothiadiazole having general formula (I), which has good solubility in the organic solvent used, have a solubility in the range of 0.05 M to 2 M, preferably 0.08 M to 1.5 M.

[0034] According to a preferred embodiment of the present invention, the ion exchange membrane is, for example, For example, ion exchange membranes such as membranes based on styrene-divinylbenzene copolymer or chloromethylstyrene-divinylbenzene copolymer containing amino groups, membranes based on poly(etheretherketone), membranes based on divinylbenzene-vinylpyridine copolymer containing quaternary pyridine groups, membranes based on aromatic polysulfone copolymers containing chloromethyl and amino groups, and membranes based on polytetrafluoroethylene (PTFE). For example, cation exchange membranes such as membranes based on tetrafluoroethylene sulfonate-based fluoropolymer-copolymers, membranes based on poly(etheretherketone), membranes based on polysulfone, membranes based on polyethylene, membranes based on polypropylene, membranes based on ethylene-propylene copolymer, membranes based on polyimide, and membranes based on polyvinyl fluoride. These can be selected from polymer films such as the following.

[0035] The commercially available anion exchange membranes that can be advantageously used in the present invention are Astom's NEOSEPTA® AMX, NEOSEPTA® AHA, NEOSEPTA® ACS, Lanxess's Ionac MA3475, DuPont's Teflon®, and Fumatech's Fumasept® FAA-3.

[0036] The cation exchange membranes that can be advantageously used in the present invention and are commercially available are Astom's NEOSEPTA® CMX and NEOSEPTA® CIMS, and DuPont's Nafion®.

[0037] Preferably, the negative electrode may comprise at least one metal such as platinum, copper, aluminum, nickel, or stainless steel; or at least one carbon-containing material such as carbon black, activated carbon, amorphous carbon, graphite, graphene, or nanostructured carbon material; or a mixture thereof. The negative electrode may be porous, grooved, or smooth.

[0038] Preferably, the positive electrode may comprise at least one metal such as platinum, copper, aluminum, nickel, or stainless steel, or at least one carbon-containing material such as carbon black, activated carbon, amorphous carbon, graphite, graphene, or nanostructured carbon material, or a mixture thereof. The positive electrode may be porous, grooved, or smooth.

[0039] Some of the benzothiadiazoles having the general formula (I) listed above are novel.

[0040] Therefore, a further object of the present invention is to provide a benzothiadiazole having general formula (Ia). [ka] Here, R1 and R2, which are identical or different from each other, represent hydrogen atoms, or C1~C 20 Preferably C1~C 10 This represents a linear or branched, saturated or unsaturated alkyl group, or a -O-R3 group, where R3 is -(CH2) n COOR4 groups are selected, where R4 is C1~C 20 Preferably C1~C 10 R3 is selected from linear or branched alkyl groups, saturated or unsaturated, where n is an integer composed of 1 to 10, preferably an integer composed of 1 to 8, or R3 is -(CH2) n Selected from OR4 groups, where R4 and n have the same meaning as above, or R3 is -(CH2CH2O) n Selected from R4 groups, where R4 and n have the same meaning as above, or R3 is -(CH2) n Selected from the CN group, where n has the same meaning as above, or R3 is -(CH2) n Selected from NR4R5 groups, where R4 and n have the same meaning as above, and R5 is C1~C 20 Preferably C1~C 10Selected from linear or branched alkyl groups, or R3 is -(CH2) n Selected from CONR4R5 groups, where R4, R5, and n have the same meaning as above for saturated or unsaturated, or R3 is -(CH2) n Selected from three Si(R4) groups, where R4 and n have the same meaning as above, or R3 is -(CH2) n Three Si(OR4) groups are selected, where R4 and n have the same meaning as above. However, at least one of R1 and R2 is different from hydrogen, and at least one of R1 and R2 is located at the 2 position of phenyl.

[0041] Benzothiadiazoles having general formula (I) can be synthesized according to procedures known in the art. In particular, compounds (2), (3), and (4) are synthesized from 2-hydroxyphenylboronic acid and 4,7-dibromobenzothiadiazole by Suzuki coupling to obtain 4,7-di(2-hydroxyphenyl)-benzothiadiazole. Suzuki coupling is highly selective, and the boronic acid derivatives are non-toxic, easy to handle, and stable. Generally, this Suzuki coupling is used, for example, with tetrakistriphenylphosphine palladium(II)[Pd(PPh] 3)4 ], [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II)[Pd(dppf)Cl2], tris(dibenzylideneacetone)-dipalladium(0) / tris(o-tolyl)phosphine[Pd2dba3 / P(o-tolyl )3The process is catalyzed by palladium-based catalysts such as tetrakis(triphenylphosphine)-palladium(II)[Pd(PPh3)4]. Specifically, tetrakis(triphenylphosphine)-palladium(II)[Pd(PPh3)4] was used, for example, by Ji C. et al. in "Dyes and Pigments" (2017), Vol. 140, pp. 203-211. Suzuki coupling requires a basic environment, and the most commonly used bases are alkali metal carbonates (potassium, sodium, cesium), potassium acetate, potassium phosphate, and potassium tert-butyrate, with potassium carbonate being specifically used. Suzuki coupling can be carried out in the presence of pure organic solvents or mixtures thereof, such as dioxane, toluene, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, water, ethyl alcohol, and isopropyl alcohol. Specifically, it is carried out in the presence of dioxane and water. Suzuki coupling is generally carried out in an inert atmosphere at a temperature of 70°C to 100°C, specifically at 80°C to 85°C.

[0042] The 4,7-di(2-hydroxyphenyl)-benzothiadiazole obtained from the above Suzuki coupling is converted to compounds (2), (3), and (4) by known Williamson etherification reactions, either by reacting with ethyl 4-bromobutyrate to obtain compound (2), by reacting with ethyl 2-bromoethyl acetate to obtain compound (3), or by reacting with 1-bromo-2-(2-methoxyethoxy)ethane to obtain compound (4), as reported, for example, by Guy K. et al. in the "Journal of Medicinal Chemistry" (2009), Vol. 52, pp. 3892-3901. The Williamson etherification reaction generally takes place in a basic environment (specifically, in the presence of potassium carbonate) and in the presence of a bipolar aprotic solvent (specifically, in the presence of dimethylformamide). The isolated products were purified by silica gel chromatography, with reaction yields ranging from 80% to 95%.

[0043] Compounds (5), (6), and (7) were synthesized from the corresponding methoxyl derivatives prepared by Suzuki coupling from 4,7-dibromobenzothiadiazole and the corresponding dimethoxyphenylboronic acid, in a manner similar to that reported above for the Suzuki coupling between 2-hydroxyphenylboronic acid and 4,7-dibromobenzothiadiazole. It is known in the literature that the methoxyl ether can be demethylated by reaction with boron tribromide, a commercially available product as a 1 M solution in dichloromethane, as described, for example, by Petronzi C. et al., "European Journal of Medicinal Chemistry" (2011), Vol. 46, pp. 488-496, to provide the corresponding hydroxyl. Specifically, 4,7-di(2,6-dimethoxyphenyl)-benzothiadiazole was obtained from 4,7-di(2,6-dimethoxyphenyl)-benzothiadiazole, 4,7-di(2,5-dihydroxyphenyl)-benzothiadiazole was obtained from 4,7-di(2,5-dimethoxyphenyl)-benzothiadiazole, and 4,7-di(2,4-dimethoxyphenyl)-benzothiadiazole was obtained from 4,7-di(2,4-dihydroxyphenyl)-benzothiadiazole. The corresponding compounds (5), (6), and (7) were obtained from these dihydroxyphenylbenzothiadiazole derivatives via a Williamson reaction with ethyl 4-bromobutyrate under basic conditions.

[0044] Alternatively, benzothiadiazoles having general formula (I) can be synthesized by micelle synthesis, for example, as described by Beverina L. et al. in "Organic Letters" (2017), Vol. 19, pp. 654-657. In this regard, for example, with respect to compound (2), 2-(propyloxycarbonylethyloxy)-1-bromobenzene was used as a starting material and reacted with pinacolbenzothiadiazole-4,7-diboronate in a solvent consisting of a 90% aqueous solution containing 2% Kolliphor and 10% toluene in a basic environment with triethylamine in the presence of [1,1'-bis(di-tert-butylphosphino)ferrocene-dichloropalladium(II)[Pd(dtbpf)Cl2] as a catalyst (micelle synthesis). The reaction was carried out at 70°C for 15 minutes. After elution on a silica gel chromatography column, product (2) was obtained in 90% yield. The advantages of this reaction are significant: (i) a reduction in toxic solvents, with water being the main solvent; (ii) a reduction in reaction time; (iii) a reduction in reaction temperature; and (iv) an increase in yield. Similarly, compound (7) was prepared using this synthetic route. Here again, micelle synthesis makes it possible to obtain the desired product in high yield in an environmentally friendly manner. [Brief explanation of the drawing]

[0045] [Figure 1] Figure 1 is a schematic diagram illustrating one embodiment of a non-aqueous redox flow battery (RFB) according to the present invention. [Figure 2] Figure 2 [the horizontal axis shows the measured potential (E) in volts (V), and the vertical axis shows the current density (J) measured in amperes / cm² (Acm⁻²)] shows a cyclic voltagram obtained from the above solution [BTD] in acetonitrile and propylene carbonate at a scanning speed of 200 mV / s. [Figure 3]Figure 3 [the horizontal axis shows the measured potential (E) in volts (V), and the vertical axis shows the current density (J) measured in amperes / cm² (Acm⁻²)] shows a cyclic voltagram obtained from the above solution [compound (2)] in acetonitrile and propylene carbonate at a scanning speed of 200 mV / s. [Figure 4] Figure 4 [the horizontal axis shows the measured potential (E) in volts (V), and the vertical axis shows the current density (J) measured in amperes / cm² (Acm⁻²)] shows a cyclic voltagram obtained from the above solution [compound (3)] in acetonitrile and propylene carbonate at a scanning speed of 200 mV / s. [Figure 5] Figure 5 [the horizontal axis shows the measured potential (E) in volts (V), and the vertical axis shows the current density (J) measured in amperes / cm² (Acm⁻²)] shows a cyclic voltagram obtained from the above solution [compound (4)] in acetonitrile and propylene carbonate at a scanning speed of 200 mV / s. [Figure 6] Figure 6 [the horizontal axis shows the measured potential (E) in volts (V), and the vertical axis shows the current density (J) measured in amperes / cm² (Acm⁻²)] shows a cyclic voltagram obtained from the above solution [compound (5)] in acetonitrile and propylene carbonate at a scanning speed of 200 mV / s. [Figure 7] Figure 7 [the horizontal axis shows the measured potential (E) in volts (V), and the vertical axis shows the current density (J) measured in amperes / cm² (Acm⁻²)] shows a cyclic voltagram obtained from the above solution [compound (6)] in acetonitrile and propylene carbonate at a scanning speed of 200 mV / s. [Figure 8] Figure 8 [the horizontal axis shows the measured potential (E) in volts (V), and the vertical axis shows the current density (J) measured in amperes / cm² (Acm⁻²)] shows a cyclic voltagram obtained from the above solution [compound (7)] in acetonitrile and propylene carbonate at a scanning speed of 200 mV / s. [Figure 9]Figure 9 [the horizontal axis shows the measured potential (E) in volts (V) and the vertical axis shows the measured current intensity (i) in amperes (A)] shows 150 consecutive redox cycles performed on the above 4,7-di[2-(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole solution [compound (2) obtained in Example 7]. [Figure 10] Figure 10 [The horizontal axis shows the measured time in seconds (t / s). The vertical axis shows the measured current intensity (i) in amperes (A).] shows the obtained charge / discharge curve. [Modes for carrying out the invention]

[0046] Here, the present invention will be described in more detail through one embodiment with reference to Figure 1 shown below.

[0047] In particular, Figure 1 is a schematic diagram showing one embodiment of a non-aqueous redox flow battery (RFB) according to the present invention. In this regard, the non-aqueous redox flow battery (RFB) 1 comprises a positive compartment 6a in which a positive electrode 6 is located and a non-aqueous liquid positive electrode electrolyte (not shown in Figure 1) flows, a negative compartment 8a in which a negative electrode 8 is located and a non-aqueous liquid negative electrode electrolyte (not shown in Figure 1) flows, and an ion exchange membrane 7 located between the positive compartment 6a and the negative compartment 8a.

[0048] Positive compartment 6a is connected by an inlet pipe 3 and a pump 4a (e.g., a peristaltic pump) and an outlet pipe 5 to a reservoir 2 containing a non-aqueous liquid cathode electrolyte comprising a solution of copper triflate or tetrafluoroborate complex [Cu(I) or Cu(II)] in at least one organic solvent, enabling the supply and discharge of the non-aqueous liquid cathode electrolyte during the operating cycle (i.e., during the charge-discharge phase).

[0049] The negative compartment 8a is connected by an inlet pipe 11 and a pump 4b (e.g., a peristaltic pump) and an outlet pipe 10 to a reservoir 12 containing a non-aqueous liquid anode electrolyte comprising a solution of at least one benzothiadiazole having general formula (I) in at least one organic solvent, thereby enabling the supply and discharge of the non-aqueous liquid anode electrolyte during the operating cycle (i.e., during the charge-discharge phase).

[0050] The voltmeter 9 is connected to the positive terminal 6 and the negative terminal 8.

[0051] During the charging phase of the non-aqueous redox flow battery (RFB) 1, a potential difference is applied between the positive and negative electrodes by a voltmeter 9. Simultaneously, the non-aqueous liquid positive electrode electrolyte is supplied from the positive electrolyte reservoir 2 to the positive compartment 6a via pump 4a, and the non-aqueous liquid negative electrode electrolyte is supplied from the negative electrolyte reservoir 12 to the negative compartment 8a via pump 4b. The non-aqueous liquid positive electrode electrolyte present in the positive compartment 6a undergoes an oxidation reaction at the positive electrode 6, and the non-aqueous liquid negative electrode electrolyte present in the negative compartment 8a undergoes a reduction reaction at the negative electrode 8. For charge equilibrium, ions involved in the oxidation-reduction reaction flow in the reverse direction through the ion exchange membrane 7. The reverse reaction occurs during the discharging phase of the non-aqueous redox flow battery (RFB) 1. The charging and discharging phases described above can be schematically represented as follows. Negative electrode: [ka] Positive electrode: [ka] battery: [ka] “carica”: charging “scarica”: electric discharge BTD = Benzothiadiazole having general formula (I), Cu = copper e- =electron

[0052] During the operating cycle (i.e., during the charge-discharge phase), both the non-aqueous liquid cathode electrolyte and the non-aqueous liquid anode electrolyte are continuously pumped into the positive and negative compartments, respectively, in order to continuously supply them to the positive and negative compartments.

[0053] The energy stored in the non-aqueous redox flow battery (RFB) 1 can be used directly to power the device in which it is inserted, or it can be transferred to the electrical network to supplement the power supply during peak usage periods. An AC / DC converter (not shown in Figure 1) may be used as needed to facilitate the transfer of energy to and from the AC power network.

[0054] The present invention is further illustrated by the following embodiments, which are provided for illustrative purposes only and do not limit the invention. [Examples]

[0055] Synthesis of 4,7-di[2-(methoxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (3)] [ka]

[0056] Synthesis of 4,7-di(2-hydroxyphenyl)-benzothiadiazole [ka]

[0057] In a 100 ml round-bottom flask equipped with a mechanical stirrer, thermometer, and coolant, a 0.08 M solution of 4,7-dibromobenzothiadiazole (Aldrich) (990 mg; 3.37 mmol) in dioxane (Aldrich) was sequentially added to a 0.08 M solution of 4,7-dibromobenzothiadiazole (Aldrich) (990 mg; 3.37 mmol) in dioxane (Aldrich) under an inert atmosphere at room temperature (25 °C) with stirring. 2-hydroxyphenylboronic acid (Aldrich) (2 g; 9.1 mmol), potassium carbonate (K2CO3) (Aldrich) (3.7 g; 27 mmol), and distilled water (12 ml) were added. After removing oxygen from the reaction environment by three vacuum / nitrogen cycles, tetrakis(triphenylphosphine)palladium(II) [Pd(PPh3)4] (Aldrich) (200 mg; 0.17 mmol) was added. The flask was immersed in an oil bath preheated to 85 °C and left at that temperature with stirring for 20 hours. Next, 50 ml of distilled water was added, and the entire mixture was extracted with ethyl ether (Aldrich) (3 × 100 ml). The resulting organic phases were combined and washed with saturated sodium chloride aqueous solution (Aldrich) until neutral, and then anhydroused with sodium sulfate (Aldrich). After removing the solvent by distillation under reduced pressure, the resulting residue was purified by elution using a silica gel chromatography column [eluent: heptane (Aldrich) / dichloromethane (Aldrich) / ethyl acetate (Aldrich) with a gradient from 91 / 6 / 3 to 82 / 12 / 6 to 70 / 20 / 10] to obtain 986 mg of 4,7-di(2-hydroxyphenyl)-benzothiadiazole (yield = 91%).

[0058] Synthesis of 4,7-di[2-(methoxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (3)] [ka]

[0059] In a 100 ml round-bottom flask equipped with a mechanical stirrer, thermometer, and coolant, a 0.05 M solution of 4,7-di(2-hydroxyphenyl)-benzothiadiazole (157.22 mg; 0.49 mmol) obtained as described above in N,N-dimethylformamide (DMF) (Aldrich) was prepared in an inert atmosphere at room temperature (25°C) with stirring. Potassium carbonate (K2CO3) (Aldrich) (276 mg; 2 mmol) was added, and after 5 minutes, ethyl 2-bromoethyl acetate (Aldrich) (220 μl; 334 mg; 2 mmol) was added. The flask was immersed in an oil bath preheated to 80°C and left at that temperature with stirring for 12 hours. Then, distilled water (100 ml) was added, and the entire solution was extracted with ethyl ether (Aldrich) (3 × 100 ml). The resulting organic phases were combined and washed with saturated sodium chloride aqueous solution (Aldrich) until neutral, and then anhydroused with sodium sulfate (Aldrich). After removing the solvent by distillation under reduced pressure, the resulting residue was purified by elution using a silica gel chromatography column [eluent: heptane (Aldrich) / dichloromethane (Aldrich) / ethyl acetate (Aldrich) gradient from 91 / 6 / 3 to 82 / 12 / 6] to obtain 229 mg of 4,7-di[2-(methoxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (3) (yield = 95%)]. [Examples]

[0060] Synthesis of 4,7-di[2-(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (2)] [ka]

[0061] In a 100 ml round-bottom flask equipped with a mechanical stirrer, thermometer, and coolant, a 0.2 M solution of 4,7-di(2-hydroxyphenyl)-benzothiadiazole (986 mg; 3.06 mmol) obtained as described in Example 1 was stirred at room temperature (25°C) in an inert atmosphere. Potassium carbonate (K2CO3) (Aldrich) (972 mg; 7.03 mmol) was added, and after 5 minutes, ethyl 4-bromobutyrate (Aldrich) (970 μl; 1322 mg; 6.73 mmol) was added. The flask was immersed in an oil bath preheated to 80°C and left at that temperature for 12 hours with stirring. Then, distilled water (100 ml) was added, and the entire solution was extracted with ethyl acetate (Aldrich) (3 × 100 ml). The resulting organic phases were combined and washed with saturated sodium chloride aqueous solution (Aldrich) until neutral, and then anhydroused with sodium sulfate (Aldrich). After removing the solvent by distillation under reduced pressure, the resulting residue was purified by elution using a silica gel chromatography column [eluent: heptane (Aldrich) / ethyl acetate (Aldrich) gradient from 80 / 20 to 70 / 30] to obtain 1300 mg of 4,7-di[2-(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (2) (yield = 80%)]. [Examples]

[0062] Synthesis of 4,7-di[2-(2-(2-methoxyethoxy)ethoxy)phenyl]-benzothiadiazole [compound (4)] [ka]

[0063] In a 100 ml round-bottom flask equipped with a mechanical stirrer, thermometer, and coolant, a 0.08 M solution of 4,7-di(2-hydroxyphenyl)-benzothiadiazole (260 mg; 0.81 mmol) obtained as described in Example 1 was stirred at room temperature (25°C) in an inert atmosphere. Potassium carbonate (K2CO3) (Aldrich) (334 mg; 2.42 mmol) was added, and after 5 minutes, 1-bromo-2-(2-methoxyethoxy)ethane (Aldrich) (323 μl; 440 mg; 2.42 mmol) was added. The flask was immersed in an oil bath preheated to 80°C and left at that temperature for 12 hours. Distilled water (50 ml) was then added, and the entire solution was extracted with ethyl acetate (Aldrich) (3 × 50 ml). The obtained organic phases were combined and washed with saturated sodium chloride aqueous solution (Aldrich) until neutral, and then anhydroused with sodium sulfate (Aldrich). After removing the solvent by distillation under reduced pressure, the resulting residue was purified by elution using a silica gel chromatography column [eluent: heptane (Aldrich) / ethyl acetate (Aldrich) with a gradient from 80 / 20 to 70 / 30 to 60 / 40] to obtain 340 mg of 4,7-di[2-(2-(2-methoxyethoxy)ethoxy)phenyl]-benzothiadiazole [compound (4) (yield = 80%)]. [Examples]

[0064] Synthesis of 4,7-di[2,6-di(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (5)] Synthesis of 4,7-di(2,6-dimethoxyphenyl)-benzothiadiazole [ka]

[0065] In a 100 ml round-bottom flask equipped with a mechanical stirrer, thermometer, and coolant, a 0.08 M solution of 4,7-dibromobenzothiadiazole (Aldrich) (500 mg; 1.7 mmol) in dioxane (Aldrich) was sequentially mixed with 2,6-dimethoxyphenylboronic acid (Aldrich) (1000 mg; 4.6 mmol), potassium carbonate (K2CO3) (Aldrich) (1.88 g; 13.6 mmol), and distilled water (7 ml) under inert atmosphere at room temperature (25°C) while stirring. After removing oxygen from the reaction environment by three vacuum / nitrogen cycles, tetrakis(triphenylphosphine)palladium(II)[Pd(PPh3)4](Aldrich) (100 mg; 0.086 mmol) was added. The flask was immersed in an oil bath preheated to 85°C and left at that temperature for 20 hours with stirring. Then, distilled water (50 ml) was added, and the entire mixture was extracted with ethyl ether (Aldrich) (3 × 50 ml). The resulting organic phases were combined, washed with distilled water until neutral, and anhydroused with sodium sulfate (Aldrich). After removing the solvent by distillation under reduced pressure, the resulting residue was purified by elution using a silica gel chromatography column [eluent: heptane (Aldrich) / dichloromethane (Aldrich) gradient from 100 / 0 to 95 / 5 to 85 / 15] to obtain 460 mg of 4,7-di(2,6-dimethoxyphenyl)-benzothiadiazole (yield = 66%).

[0066] Synthesis of 4,7-di(2,6-dihydroxyphenyl)-benzothiadiazole [ka]

[0067] In a 100 ml round-bottom flask equipped with a mechanical stirrer, thermometer, and coolant, under an inert atmosphere, while stirring at -78°C, a 0.09 M solution of 4,7-di(2,6-dimethoxyphenyl)-benzothiadiazole (439 mg; 1.07 mmol) obtained as described above in anhydrous dichloromethane (CH2Cl2) (Aldrich) was slowly added dropwise to a 1 M solution of boron tribromide (BBR3) (Aldrich) in anhydrous dichloromethane (CH2Cl2) (Aldrich) (16 ml; 16 mmol). The temperature was slowly and naturally raised to room temperature (25°C). After the mixture was cooled to -78°C, ethanol (Aldrich) (25 ml) was slowly added dropwise. Next, the temperature was returned to room temperature (25°C), the solvent was removed by distillation under reduced pressure, distilled water (50 ml) was added, and the entire mixture was extracted with ethyl acetate (Aldrich) (3 x 50 ml). The obtained organic phases were combined, washed with an aqueous sodium chloride solution (Aldrich) until neutral, and anhydroused with sodium sulfate (Aldrich). The resulting residue was purified by silica gel chromatography column (eluent: heptane (Aldrich) / ethyl acetate (Aldrich), ratio 60 / 40 (v / v)) to obtain 289.4 mg of 4,7-di(2,6-dihydroxyphenyl)-benzothiadiazole (yield = 77%).

[0068] Synthesis of 4,7-di[2,6-di(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (5)] [ka]

[0069] In a 100 ml round-bottom flask equipped with a mechanical stirrer, thermometer, and coolant, a 0.05 M solution of 4,7-di(2,6-dihydroxyphenyl)-benzothiadiazole (289.4 mg; 0.82 mmol) obtained as described above in N,N-dimethylformamide (DMF) (Aldrich) was stirred in an inert atmosphere at room temperature (25°C). Potassium carbonate (K2CO3) (Aldrich) (959 mg; 4.9 mmol) was added, and after 5 minutes, ethyl 4-bromobutyrate (Aldrich) (704 μl; 1322 mg; 4.9 mmol) was added. The flask was immersed in an oil bath preheated to 80°C and left at that temperature for 12 hours with stirring. Then, distilled water (50 ml) was added, and the entire solution was extracted with ethyl acetate (Aldrich) (3 × 50 ml). The resulting organic phases were combined, washed with distilled water until neutral, and anhydroused with sodium sulfate (Aldrich). After removing the solvent by distillation under reduced pressure, the resulting residue was purified by elution using a silica gel chromatography column (eluent: heptane (Aldrich) / ethyl acetate (Aldrich) in a 70 / 30 v / v ratio) to obtain 380 mg of 4,7-di[2,6-di(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (5) (yield = 57%)]. [Examples]

[0070] Synthesis of 4,7-di[2,5-di(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (6)] Synthesis of 4,7-di(2,5-dimethoxyphenyl)benzothiadiazole [ka]

[0071] In a 100 ml round-bottom flask equipped with a mechanical stirrer, thermometer, and coolant, a 0.08 M solution of 4,7-dibromobenzothiadiazole (Aldrich) (700 mg; 2.4 mmol) in dioxane (Aldrich) was sequentially added to a 0.08 M solution of 4,7-dibromobenzothiadiazole (Aldrich) (700 mg; 2.4 mmol) in dioxane (Aldrich). This solution was then mixed with 2,5-dimethoxyphenylboronic acid (Aldrich) (1180 mg; 6.5 mmol), potassium carbonate (K2CO3) (Aldrich) (2.65 g; 19.2 mmol), and distilled water (10 ml). After removing oxygen from the reaction environment by three vacuum / nitrogen cycles, tetrakis(triphenylphosphine)palladium(II) [Pd(PPh3)4] (Aldrich) (140 mg; 0.121 mmol). The flask was immersed in an oil bath preheated to 85 °C and left at that temperature for 20 hours with stirring. Next, 100 ml of distilled water was added, and the entire mixture was extracted with ethyl ether (Aldrich) (3 × 100 ml). The resulting organic phases were combined, washed with distilled water until neutral, and anhydroused with sodium sulfate (Aldrich). After removing the solvent by distillation under reduced pressure, the resulting residue was purified by elution using a silica gel chromatography column [eluent: heptane (Aldrich) / dichloromethane (Aldrich) gradient from 100 / 0 to 95 / 5 to 90 / 10 to 85 / 15] to obtain 880 mg of 4,7-di(2,5-dimethoxyphenyl)-benzothiadiazole (yield = 90%).

[0072] Synthesis of 4,7-di(2,5-dihydroxyphenyl)-benzothiadiazole [ka]

[0073] In a 100 ml round-bottom flask equipped with a mechanical stirrer, thermometer, and coolant, a 0.09 M solution of 4,7-di(2,5-dimethoxyphenyl)-benzothiadiazole (738 mg; 1.8 mmol) obtained as described above in anhydrous dichloromethane (CH2Cl2) (Aldrich) was slowly added dropwise to a 1 M solution of boron tribromide (BBR3) (Aldrich) in anhydrous dichloromethane (CH2Cl2) (Aldrich) (27 ml; 27 mmol) while stirring at -78°C under an inert atmosphere. The temperature was slowly and naturally raised to room temperature (25°C). After the mixture cooled to -78°C, ethanol (25 ml) was slowly added dropwise. Next, the temperature was returned to room temperature (25°C), the solvent was removed by distillation under reduced pressure, distilled water (50 ml) was added, and the entire mixture was extracted with ethyl acetate (Aldrich) (3 x 50 ml). The obtained organic phases were combined, washed with an aqueous sodium chloride solution (Aldrich) until neutral, and anhydroused with sodium sulfate. The resulting residue was purified by silica gel chromatography column (eluent: heptane (Aldrich) / ethyl acetate (Aldrich), ratio 60 / 40 (v / v)) to obtain 557.4 mg of 4,7-di(2,5-dihydroxyphenyl)-benzothiadiazole (yield = 87.2%).

[0074] Synthesis of 4,7-di[2,5-di(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (6)] [ka]

[0075] In a 100 ml round-bottom flask equipped with a mechanical stirrer, thermometer, and coolant, a 0.1 M solution of 4,7-di(2,5-dihydroxyphenyl)-benzothiadiazole (557.4 mg; 1.57 mmol) obtained as described above was prepared in an inert atmosphere at room temperature (25°C) with stirring. Potassium carbonate (K2CO3) (Aldrich) (1300 mg; 9.4 mmol) was added, and after 5 minutes, ethyl 4-bromobutyrate (1.35 ml; 1322 mg; 9.4 mmol) was added. The flask was immersed in an oil bath preheated to 85°C and left at that temperature with stirring for 12 hours. Distilled water (50 ml) was then added, and the entire solution was extracted with ethyl acetate (Aldrich) (3 × 50 ml). The resulting organic phases were combined, washed with distilled water until neutral, and anhydroused with sodium sulfate (Aldrich). After removing the solvent by distillation under reduced pressure, the resulting residue was purified by elution using a silica gel chromatography column (eluent: heptane (Aldrich) / ethyl acetate (Aldrich) in a 70 / 30 v / v ratio) to obtain 888 mg of 4,7-di[2,5-di(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (6) (yield = 70%)]. [Examples]

[0076] Synthesis of 4,7-di[2,4-di(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (7)] Synthesis of 4,7-di(2,4-dimethoxyphenyl)-benzothiadiazole [ka]

[0077] In a 100 ml round-bottom flask equipped with a mechanical stirrer, thermometer, and coolant, a 0.08 M solution of 4,7-dibromobenzothiadiazole (Aldrich) (705 mg; 2.4 mmol) in dioxane (Aldrich) was sequentially added to a 0.08 M solution of 4,7-dibromobenzothiadiazole (Aldrich) (705 mg; 2.4 mmol) in dioxane (Aldrich) under an inert atmosphere at room temperature (25 °C) with stirring. 2,4-dimethoxyphenylboronic acid (Aldrich) (1170 mg; 6.43 mmol), potassium carbonate (K2CO3) (Aldrich) (6.5 g; 19.2 mmol), and distilled water (10 ml) were added. After removing oxygen from the reaction environment by three vacuum / nitrogen cycles, tetrakis(triphenylphosphine)palladium(II) [Pd(PPh3)4] (Aldrich) (140 mg; 0.121 mmol) was added. The flask was immersed in an oil bath preheated to 85 °C and left at that temperature with stirring for 20 hours. Next, 50 ml of distilled water was added, and the entire mixture was extracted with ethyl ether (Aldrich) (3 × 50 ml). The resulting organic phases were combined, washed with distilled water until neutral, and anhydroused with sodium sulfate (Aldrich). After removing the solvent by distillation under reduced pressure, the resulting residue was purified by elution using a silica gel chromatography column (eluent: heptane (Aldrich) / dichloromethane (Aldrich) gradient from 100 / 0 to 95 / 5, 90 / 10, 85 / 15, 80 / 20, and 70 / 30) to obtain 832 mg of 4,7-di(2,4-dimethoxyphenyl)-benzothiadiazole (yield = 85%).

[0078] Synthesis of 4,7-di(2,4-dihydroxyphenyl)-benzothiadiazole [ka]

[0079] In a 100 ml round-bottom flask equipped with a mechanical stirrer, thermometer, and coolant, under an inert atmosphere, while stirring at -78°C, a 0.09 M solution of 4,7-di(2,4-dimethoxyphenyl)-benzothiadiazole (330 mg; 0.8 mmol) obtained as described above in anhydrous dichloromethane (CH2Cl2) (Aldrich) was slowly added dropwise to a 1 M solution of boron tribromide (BBR3) (Aldrich) in anhydrous dichloromethane (CH2Cl2) (Aldrich) (12 ml; 12 mmol). The temperature was slowly and naturally raised to room temperature (25°C). After the mixture cooled to -78°C, ethanol (Aldrich) (25 ml) was slowly added dropwise. Next, the temperature was returned to room temperature (25°C), the solvent was removed by distillation under reduced pressure, distilled water (50 ml) was added, and the entire mixture was extracted with ethyl acetate (Aldrich) (3 x 50 ml). The obtained organic phases were combined, washed with an aqueous sodium chloride solution (Aldrich) until neutral, and anhydroused with sodium sulfate (Aldrich). The resulting residue was purified by silica gel chromatography column (eluent: heptane (Aldrich) / ethyl acetate (Aldrich), ratio 60 / 40 (v / v)) to obtain 270 mg of 4,7-di(2,4-dihydroxyphenyl)-benzothiadiazole (yield = 95%).

[0080] Synthesis of 4,7-di[2,4-di(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (7)] [ka]

[0081] In a 100 ml round-bottom flask equipped with a mechanical stirrer, thermometer, and coolant, a 0.076 M solution of 4,7-di(2,4-dihydroxyphenyl)-benzothiadiazole (268 mg; 0.76 mmol) obtained as described above in N,N-dimethylformamide (DMF) (Aldrich) was stirred in an inert atmosphere at room temperature (25°C). Potassium carbonate (K2CO3) (Aldrich) (626 mg; 4.54 mmol) was added, and after 5 minutes, ethyl 4-bromobutyrate (Aldrich) (652 μl; 889 mg; 4.54 mmol) was added. The flask was immersed in an oil bath preheated to 80°C and left at that temperature for 12 hours with stirring. Then, distilled water (50 ml) was added, and the entire solution was extracted with ethyl acetate (Aldrich) (3 × 50 ml). The obtained organic phases were combined, washed with distilled water until neutral, and anhydroused with sodium sulfate (Aldrich). After removing the solvent by distillation under reduced pressure, the resulting residue was purified by elution using a silica gel chromatography column (eluent: heptane (Aldrich) / ethyl acetate (Aldrich) 70 / 30 v / v ratio) to obtain 490 mg of 4,7-di[2,4-di(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (7) (yield = 80%)]. [Examples]

[0082] Synthesis of 4,7-di[2-(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (2)] - Suzuki - Micelle synthesis [ka]

[0083] In a 100 ml round-bottom flask equipped with a mechanical stirrer, thermometer, and coolant, under an inert atmosphere, at room temperature (25°C), while stirring, triethylamine (TEA) was added to a suspension of 2-(propyloxycarbonylethyloxy)-1-bromobenzene (Aldrich) (1000 mg, 3.5 mmol), pinacol 4,7-benzothiadiazole diboronate (Aldrich) (630 mg, 1.62 mmol), and [1,1'-bis(di-tert-butylphosphino)ferrocene]-dichloropalladium(II)[Pd(dtbpf)Cl2](Aldrich) (24 mg, 0.037 mmol) in a 9:1 (v / v) mixture of Kolliphor® EL (2% by weight solution in deionized water) (Aldrich) and toluene (Aldrich). Aldrich (1022 mg, 1.4 ml, 10 mmol) was added. The resulting reaction mixture was heated to 70°C and held at that temperature for 15 minutes with stirring. Distilled water (50 ml) was then added, and the entire mixture was extracted with ethyl acetate (Aldrich) (3 × 50 ml). The resulting organic phases were combined, washed with distilled water until neutral, and anhydroused with sodium sulfate (Aldrich). After removing the solvent by distillation under reduced pressure, the resulting residue was purified by silica gel chromatography column (eluent: heptane (Aldrich) / ethyl acetate (Aldrich), ratio 80 / 20 (v / v)) to obtain 797.8 mg of 4,7-di[2-(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (2) (yield = 90%)]. [Examples]

[0084] Synthesis of 4,7-di[2,4-di(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (7)] - Suzuki - Micelle synthesis [ka]

[0085] In a 100 ml round-bottom flask equipped with a mechanical stirrer, thermometer, and coolant, under an inert atmosphere, at room temperature (25°C), while stirring, 2,4-(propyloxycarbonylethyloxy)-1-bromobenzene (Aldrich) (2400 mg, 5.8 mg) was added to 4 ml of a 9:1 (v / v) mixture of Kolliphor® EL (2% by weight solution in deionized water) (Aldrich) and toluene (Aldrich). Triethylamine (Aldrich) (1752 mg, 2.4 ml, 17.3 mmol) was added to a suspension of pinacol 4,7-benzothiadiazole diboronate (Aldrich) (1028 mg, 2.6 mmol) and [1,1'-bis(di-tert-butylphosphino)ferrocene]-dichloropalladium(II)[Pd(dtbpf)Cl2] (Aldrich) (42 mg, 0.064 mmol). The resulting reaction mixture was heated to 70°C and held at that temperature for 15 minutes with stirring.

[0086] Next, 100 ml of distilled water was added, and the entire mixture was extracted with ethyl acetate (Aldrich) (3 × 100 ml). The resulting organic phases were combined, washed with distilled water until neutral, and anhydroused with sodium sulfate (Aldrich). After removing the solvent by distillation under reduced pressure, the resulting residue was purified by silica gel chromatography column (eluent: heptane (Aldrich) / ethyl acetate (Aldrich), gradient from 80 / 20 to 70 / 30 to 65 / 35) to obtain 2140 mg of 4,7-di[2,4-di(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (7) (yield = 100%)]. [Examples]

[0087] Cyclic voltammetry measurement

[0088] Cyclic voltammetry measurements were performed using a half-cell with a three-electrode configuration: a glassy carbon working electrode, a platinum counter electrode, and a silver / silver chloride (Ag / AgCl) reference electrode. Redox potential E °’ Ox / Red Forward peak (Epf ) and return peak (E pr Obtained from the position of ).

number

[0089] The evaluation was performed using an Autolab PGSTAT 128N analyzer at scanning speeds of 10, 20, 50, 70, 100, and 200 mV / s. All evaluations were performed three times at room temperature (25°C). For this purpose, a solution containing the following was used. Benzothiadiazole (1) (Aldrich) in acetonitrile (Aldrich) (5x10 -3 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) (0.1M) (non-aqueous liquid anode electrolyte for the negative compartment) (BTD), Benzothiadiazole (1) (Aldrich) in propylene carbonate (Aldrich) (5x10 -3 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) (0.1M) (non-aqueous liquid anode electrolyte for the negative compartment) (BTD), 4,7-di[2-(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound obtained in Example 7 (2)] (5x10) in acetonitrile (Aldrich) -3 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) (0.1M) (non-aqueous liquid anode electrolyte for the negative compartment) (BTD), 4,7-di[2-(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound obtained in Example 7 (2)] (5x10) in propylene carbonate (Aldrich) -3 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) (0.1M) (non-aqueous liquid anode electrolyte for the negative compartment) [BTD(2)], 4,7-di[2-(methoxycarbonylethyloxy)phenyl]-benzothiadiazole [compound obtained in Example 1 (3)] (5x10) in acetonitrile (Aldrich) -3 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) (0.1M) (non-aqueous liquid anode electrolyte for the negative compartment) [BTD(3)], 4,7-di[2-(methoxycarbonylethyloxy)phenyl]-benzothiadiazole [compound obtained in Example 1 (3)] (5x10) in propylene carbonate (Aldrich) -3 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) (0.1M) (non-aqueous liquid anode electrolyte for the negative compartment) [BTD(3)], 4,7-di[2-(2-(2-methoxyethoxy)ethoxy)phenyl]-benzothiadiazole [compound obtained in Example 3 (4)] (5x10) in acetonitrile (Aldrich) -3 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) (0.1M) (non-aqueous liquid anode electrolyte for the negative compartment) [BTD(4)], 4,7-di[2-(2-(2-methoxyethoxy)ethoxy)phenyl]-benzothiadiazole [compound obtained in Example 3 (4)] (5x10) in propylene carbonate (Aldrich) -3 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) (0.1M) (non-aqueous liquid anode electrolyte for the negative compartment) [BTD(4)], 4,7-di[2,6-di(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound obtained in Example 4 (5)] (5x10) in acetonitrile (Aldrich) -3 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) (0.1M) (non-aqueous liquid anode electrolyte for the negative compartment) [BTD(5)], 4,7-di[2,6-di(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound obtained in Example 4 (5)] (5x10) in propylene carbonate (Aldrich) -3 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) (0.1M) (non-aqueous liquid anode electrolyte for the negative compartment) [BTD(5)], 4,7-di[2,5-di(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound obtained in Example 5 (6)] (5x10) in acetonitrile (Aldrich) -3 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) (0.1M) (non-aqueous liquid anode electrolyte for the negative compartment) [BTD(6)], 4,7-di[2,5-di(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound obtained in Example 5 (6)] (5x10) in propylene carbonate (Aldrich) -3 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) (0.1M) (non-aqueous liquid anode electrolyte for the negative compartment) [BTD(6)], 4,7-di[2,4-di(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound obtained in Example 8 (7)] (5x10) in acetonitrile (Aldrich) -3 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) (0.1M) (non-aqueous liquid anode electrolyte for the negative compartment) [BTD(7)], 4,7-di[2,4-di(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound obtained in Example 8 (7)] (5x10) in propylene carbonate (Aldrich) -3 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) (0.1M) (non-aqueous liquid anode electrolyte for the negative compartment) [BTD(7)], Copper(II) trifluoromethanesulfonic acid [Cu(CF3SO3)2] (Aldrich) in acetonitrile (Aldrich) (5x10 -4 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) (0.1M) (non-aqueous liquid cathode electrolyte for the positive compartment) (Cu triflate), Tetrakisacetonitrile copper(I) tetrafluoroborate [Cu(NCCH3)4·BF4] (Aldrich) in acetonitrile (5x10) -4 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) (0.1M) (non-aqueous liquid cathode electrolyte for the positive compartment) [Cu(I) tetrafluoroborate], Tetrakisacetonitrile copper(I) triflate [Cu(NCCH3)4·CF3SO3] (Aldrich) in propylene carbonate (5x10 -4 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) (0.1M) (non-aqueous liquid cathode electrolyte for the positive compartment) [Cu(I)].

[0090] The obtained values ​​are shown in Table 2.

[0091] [Table 2]

[0092] Figures 2-8 [The horizontal axis shows the measured potential (E) in volts (V), and the vertical axis shows amperes / cm²]. 2 (Acm -2 The graph shows the current density (J) measured by [ ], and the cyclic voltagram obtained at a scanning speed of 200 mV / s from the above solutions [BTD and compounds (2)~(7)] in acetonitrile and propylene carbonate.

[0093] For example, considering a solution of compound (2) in acetonitrile, calculations according to the following formula show that a high potential difference (E°) of 2.53V is obtained in an open circuit. E° = (E°1) - (E°2) Here, (E°1) is the redox potential of (Cu triflate) calculated as above, and is 0.62 V vs (Fc / Fc + It becomes equal to ). (E°2) is the redox potential of the various solutions calculated as described above and reported in Table 2 (Example 2 is equal to -1.91). [Examples]

[0094] Stability testing using cyclic voltammetry

[0095] Stability testing was performed using the same electrochemical cell as in Example 9.

[0096] For this purpose, 4,7-di[2-(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound obtained in Example 2 or 7 (2)] (1x10) in acetonitrile (Aldrich) -3 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) 0.1M (non-aqueous liquid anode electrolyte for the negative compartment), A solution containing the following was used.

[0097] Figure 9 [the horizontal axis shows the measured potential (E) in volts (V), and the vertical axis shows the measured current intensity (i) in amperes (A)] shows 150 consecutive redox cycles performed on the above 4,7-di[2-(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole solution [compound (2) obtained in Example 7]. The cycles were found to be superimposed, which means that there was no material deposition on the electrodes due to parasitic or polymerization reactions, and the formed radicals were stable. [Examples]

[0098] Non-aqueous redox flow battery (RFB) charge / discharge test [Electrolyte: 4,7-di[2-(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (2)] and tetrakisacetonitrile tetrafluoroborate copper(I) [Cu(NCCH3)4·BF4]]

[0099] The charge / discharge test was performed at approximately 0.07 cm. 2 Approximately 0.8 cm² is placed between two platinum electrodes (Metrohm) having an equal surface area. 2 The procedure was carried out using an electrochemical cell having a Teflon® film (DuPont) with a surface area equal to . The electrochemical cell was then assembled and sealed in a container containing argon (Ar).

[0100] For this purpose, Reduced benzothiadiazole [(BTD(2) ·- To obtain ), 4,7-di[2-(propyloxycarbonylethyloxy)phenyl]-benzothiadiazole [compound (2) obtained in Example 7] (1x10) was degassed with argon (Ar) and subjected to electrolysis in acetonitrile (Aldrich). -3 M) and tetrabutylammonium tetrafluoroborate (TBABF4) (Aldrich) (0.1M) (non-aqueous liquid anode electrolyte for the negative compartment), Tetrakisacetonitrile copper(I) tetrafluoroborate [Cu(NCCH3)4·BF4] (1x10) in acetonitrile (Aldrich) degassed with argon (Ar). -3 M) and tetrabutylammonium tetrafluoroborate (TBA BF4) (Aldrich) (0.1M) (non-aqueous liquid cathode electrolyte for the positive compartment) (Cu triflate) A solution containing [the substance] was used.

[0101] Six ml of the above solution was introduced into each compartment.

[0102] The tests were conducted at room temperature (25°C) using the Autolab PGSTAT 128N (Metrohom) potentiostat / galvanostat.

[0103] Charge and discharge curves were performed to evaluate the performance of the electrolyte in the cells. The tests were conducted in constant potential mode, applying a charging potential of 2.5V and a discharging potential of 0.5V. Each potential was applied for 240 seconds.

[0104] Figure 10 [The horizontal axis shows the measured time in seconds (t / s). The vertical axis shows the measured current intensity (i) in amperes (A).] shows the obtained charge / discharge curve. During discharge, electrons enter the negative electrode [(BTD(2) ·- Because current moves from the ) to the positive electrode (Cu), the current has a negative sign. Conversely, during charging, the current has a positive sign. Since the current intensity value is stable, both species are characterized by good stability during the oxidation-reduction cycle (or redox cycle).

Claims

1. Non-aqueous redox flow battery (RFB), A positive compartment is where the positive electrode is placed and a non-aqueous liquid positive electrode electrolyte flows through it, A negative compartment is located where the negative electrode is positioned and through which a non-aqueous liquid negative electrode electrolyte flows, An ion exchange membrane is disposed between the positive compartment and the negative compartment, Equipped with, The non-aqueous liquid cathode electrolyte comprises a solution of copper triflate or tetrafluoroborate complex [Cu(I) or Cu(II)] in at least one organic solvent. The non-aqueous liquid negative electrode electrolyte comprises a solution of at least one benzothiadiazole having general formula (I) in at least one organic solvent, 【Chemistry 1】 Here, R ｎ , ３ , ２０ , ２ , １ , ５ , ４ , ５ , ｎ , ｎ , ２ , ３ , ４ , ４ , ２ , ｎ , ４ , ３ , ２ , ３ , ４ , ２０ , １ , ２ , ４ , ４ , ３ , ５ , ４ , ｎ , ２ and R ２ represents a hydrogen atom, or a linear or branched, saturated or unsaturated alkyl group of C １ to C ２０ , or represents an -O-R ３ group, where R ３ is selected from linear or branched, saturated or unsaturated alkyl groups of C １ to C ２０ , or R ３ is selected from the -(CH ２ ) ｎ COOR ４ group, where R ４ is selected from linear or branched, saturated or unsaturated alkyl groups of C １ to C ２０ , n is an integer composed of 1 to 10, or R ３ is selected from the -(CH ２ ) ｎ OR ４ group, R ４ and n have the same meaning as above, or R ３ is selected from the -(CH ２ CH ２ O) ｎ R ４ group, R ４ and n have the same meaning as above, or R ３ is selected from the -(CH ２ ) ｎ CN group, n has the same meaning as above, or R ３ is selected from the -(CH ２ ) ｎ NR ４ R ５ group, where R ４ and n have the same meaning as above, R ５ is selected from linear or branched alkyl groups of C １ to C ２０ , or R ３ is selected from the -(CH ２ ) ｎ CONR ４ R<00​ ４ , R ５ And n has the same meaning as above, whether saturated or unsaturated, or R ３ is, -(CH ２ ) ｎ Si(R ４ ) ３ Selected from the base, where R ４ And n have the same meaning as above, or R ３ is, -(CH ２ ) ｎ Si ( OR ４ ) ３ Selected from the base, where R ４ And n has the same meaning as above, However, R １ and R ２ At least one of them is different from hydrogen, R １ and R ２ At least one of them is at the 2-position of phenyl, Non-aqueous redox flow battery (RFB).

2. The copper triflate or tetrafluoroborate complex [Cu(I) or Cu(II)] is tetrakisacetonitrile copper(I) triflate [Cu(NCCH ３ ) ４ CF ３ SO ３ ], copper(II) trifluoromethanesulfonate [Cu(CF ３ SO ３ ) ２ ], tetrakisacetonitrile copper(I) tetrafluoroborate [Cu(NCCH ３ ) ４ BF ４ A non-aqueous redox flow battery (RFB) according to claim 1, selected from ] or a mixture thereof.

3. The above general formula (I) is, Identical or different from each other, R １ and R ２ However, this represents a hydrogen atom, or -OR ３ It represents the base, and here, R ３ is, -(CH ２ ) ｎ COOR ４ Selected from the base, R ４ is C １ ~C ２０ Selected from linear or branched alkyl groups, saturated or unsaturated, where n is an integer composed of 1 to 10, or R ３ is, -(CH ２ CH ２ O) ｎ R ４ Selected from the base, R ４ And n has the same meaning as above, However, R １ and R ２ at least one of which is different from hydrogen, and R １ and R ２ at least one of which is at the 2-position of phenyl, A non-aqueous redox flow battery (RFB) according to claim 1 or 2.

4. The above general formula (I) is, Identical or different from each other, R １ and R ２ The non-aqueous redox flow battery (RFB) according to claim 3, wherein the group represents a propyloxycarbonylethyloxy group, a methoxycarbonylethyloxy group, and a methoxyethoxyethyloxy group.

5. At least one of the non-aqueous liquid positive electrode electrolyte and the non-aqueous liquid negative electrode electrolyte is lithium tetrafluoroborate (LiBF ４ ), lithium hexafluorophosphate (LiPF ６ ), lithium perchlorate (LiClO ４ ), methyltrifluoromethanesulfonate (LiCF ３ SO ３ ), lithium bis(trifluoromethylsulfonyl)imide [Li(CF ３ SO ２ ), ２ N], tetraethylammonium tetrafluoroborate (TEABF ４ ), tetrabutylammonium tetrafluoroborate (TBABF ４ ), or a mixture thereof, and comprises at least one supporting electrolyte. The non-aqueous redox flow battery (RFB) according to claim 1.

6. The at least one supporting electrolyte is lithium tetrafluoroborate (LiBF ４ ), tetrabutylammonium tetrafluoroborate (TBABF ４ A non-aqueous redox flow battery (RFB) according to claim 5, selected from ).

7. The non-aqueous redox flow battery (RFB) according to claim 1, wherein the organic solvent is selected from acetonitrile, dimethylacetamide, diethyl carbonate, dimethyl carbonate, γ-butyrolactone (GBL), propylene carbonate (PC), ethylene carbonate (EC), N-methyl-2-pyrrolidone (NMP), fluoroethylene carbonate, N,N-dimethylacetamide, or a mixture thereof.

8. The non-aqueous redox flow battery (RFB) according to claim 7, wherein the organic solvent is selected from acetonitrile and propylene carbonate (PC).

9. The ion exchange membrane is Ion exchange membranes selected from: membranes based on styrene-divinylbenzene copolymer or chloromethylstyrene-divinylbenzene copolymer containing amino groups; membranes based on poly(ether ether ketone); membranes based on divinylbenzene-vinylpyridine copolymer containing quaternary pyridine groups; membranes based on aromatic polysulfone copolymers containing chloromethyl and amino groups; and membranes based on polytetrafluoroethylene (PTFE). Cation exchange membranes selected from tetrafluoroethylene sulfonate-based fluoropolymer-copolymer membranes, poly(ether-ether-ketone)-based membranes, polysulfone-based membranes, polyethylene-based membranes, polypropylene-based membranes, ethylene-propylene copolymer-based membranes, polyimide-based membranes, and polyvinyl fluoride-based membranes. A non-aqueous redox flow battery (RFB) according to claim 1, selected from polymer membranes selected from.

10. A non-aqueous liquid anode electrolyte for a non-aqueous redox flow battery (RFB), wherein the non-aqueous liquid anode electrolyte comprises a solution of at least one benzothiadiazole having general formula (Ia), 【Chemistry 2】 Here, R is either identical or different from each other. １ and R ２ represents a hydrogen atom, or C １ ~C ２０ It represents a linear or branched, saturated or unsaturated alkyl group, or -O-R ３ It represents the base, and here, R ３ C １ ~C ２０ Selected from linear or branched, saturated or unsaturated alkyl groups, or R ３ ha- (CH ２ ) ｎ COOR ４ Selected from the base, where R ４ C １ ~C ２０ Selected from linear or branched alkyl groups, saturated or unsaturated, where n is an integer composed of 1 to 10, or R ３ ha- (CH ２ ) ｎ OR ４ Selected from the base, R ４ And n have the same meaning as above, or R ３ is, -(CH ２ CH ２ O) ｎ R ４ Selected from the base, R ４ And n have the same meaning as above, or R ３ is, -(CH ２ ) ｎ Selected from CN groups, where n has the same meaning as above, or R ３ is, -(CH ２ ) ｎ NR ４ R ５ Selected from the base, where R ４ And n has the same meaning as above, R ５ C １ ~C ２０ Selected from linear or branched alkyl groups, saturated or unsaturated, or R ３ is, -(CH ２ ) ｎ CONR ４ R ５ Selected from the base, where R ４ , R ５ And n have the same meaning as above, or R ３ is, -(CH ２ ) ｎ Si(R ４ ) ３ Selected from the base, where R ４ And n have the same meaning as above, or R ３ is, -(CH ２ ) ｎ Si ( OR ４ ) ３ Selected from the base, where R ４ And n has the same meaning as above, However, R １ and R ２ At least one of them is different from hydrogen, R １ and R ２ At least one of them is at the 2-position of phenyl, Non-aqueous liquid anode electrolyte.

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