Organic positive electrode active material for aqueous redox flow battery

Abstract

An organic positive electrode active material for aqueous redox flow batteries, and more particularly, to technology of applying an organic positive electrode active material to make up for the drawbacks of conventional aqueous redox flow batteries. An aqueous redox flow battery to which a particular positive electrode active material is applied has no problems regarding metal deposition, and can also be useful in realizing a high energy density because the positive electrode active material may be used at high concentration due to an increase in solubility in a solvent, attaining a high working voltage, and enhancing energy efficiency. Also, the aqueous redox flow battery has excellent economic feasibility because an expensive organic electrolyte is not used.

Claims

1. A redox flow battery which is charged/discharged, comprising: a positive electrode cell comprising a positive electrode and a positive electrode electrolyte; a negative electrode cell comprising a negative electrode and a negative electrode electrolyte; an ion exchange membrane disposed between the positive electrode cell and the negative electrode cell; and a positive electrode electrolyte tank configured to supply the positive electrode electrolyte to the positive electrode cell by driving a pump and having the positive electrode electrolyte stored therein and a negative electrode electrolyte tank configured to supply the negative electrode electrolyte to the negative electrode cell by driving a pump and having the negative electrode electrolyte stored therein, wherein each of the positive electrode electrolyte and the negative electrode electrolyte comprises an electrode active material and an aqueous solvent, wherein the positive electrode active material included in the positive electrode electrolyte comprises a compound represented by the following Formula 1, and does not comprise vanadium ions, and wherein the negative electrode electrolyte contains positive bivalent vanadium ions (V.sup.2+) and positive trivalent vanadium ions (V.sup.3+): ##STR00004## wherein R.sub.1 is NH.sub.2, and R.sub.2 to R.sub.5 are H.

2. The redox flow battery of claim 1, wherein the positive electrode active material is included at a concentration of 0.01 to 5 M.

3. The redox flow battery of claim 2, wherein the aqueous solvent of the positive electrode electrolyte comprises one or more selected from the group consisting of H.sub.2SO.sub.4, K.sub.2SO.sub.4, Na.sub.2SO.sub.4, H.sub.3PO.sub.4, H.sub.4P.sub.2O.sub.7, K.sub.2HPO.sub.4, Na.sub.3PO.sub.4, K.sub.3PO.sub.4, HNO.sub.3, KNO.sub.3, NaNO.sub.3, and a combination thereof.

Description

DESCRIPTION OF DRAWINGS

(1) FIG. 1 is data obtained from a cyclic voltammetry test on a single cell to which a 4-aminophenol aqueous solution according to the present invention is applied as a positive electrode electrolyte.

(2) FIG. 2 is an image of the 4-aminophenol aqueous solution according to the present invention before and after the cyclic voltammetry test.

(3) FIG. 3 is a charge/discharge voltage-time graph of the single cell to which the 4-aminophenol aqueous solution according to the present invention is applied as the positive electrode electrolyte.

(4) FIG. 4 is current efficiency data obtained during a charge/discharge cycle of the single cell to which the 4-aminophenol aqueous solution according to the present invention is applied as the positive electrode electrolyte.

BEST MODE

(5) When a redox flow battery is a vanadium-based redox flow battery in a typical shape, the battery may be charged and discharged by circulating a positive electrode electrolyte, which includes a sulfuric acid electrolyte containing tetravalent vanadium ions (V.sup.4+) and pentavalent vanadium ions (V.sup.5+), into a positive electrode cell and circulating a negative electrode electrolyte, which contains trivalent vanadium ions (V.sup.3+) and bivalent vanadium ions (V.sup.2+), into a negative electrode cell. In this case, because the vanadium ions release electrons, V.sup.4+ is oxidized into V.sup.5+ during a charging cycle in the positive electrode cell, and V.sup.3+ is reduced into V.sup.2+ by the electrons returned through an outside line in the negative electrode cell.

(6) However, pentavalent vanadium ions in the positive electrode electrolyte generated in the positive electrode precipitate in the form of V.sub.2O.sub.5 at a temperature of approximately 40° C. or higher. In this case, the resulting precipitates have a problem in that the precipitates are not re-dissolved in an electrolyte.

(7) To solve the above problems, the present invention provides an organic positive electrode active material for aqueous redox flow batteries, which includes a compound represented by the following Formula 1, in order to replace vanadium used as a conventional positive electrode active material.

(8) ##STR00002##

(9) wherein R.sub.1 to R.sub.5 are the same or different from each other, and each independently represent H, NH.sub.2, NO.sub.2, X, CX.sub.3, or CN, and X is a halogen element, provided that at least one of R.sub.1 to R.sub.5 is not H.

(10) Preferably, in the compound represented by Formula 1, R.sub.1 is an electron-donating group, that is, an NH.sub.2 functional group, or an electron-withdrawing group, that is, NO.sub.2 or a halogen (F, Cl, Br, or I), and R.sub.2 to R.sub.5 are H. For example, the organic positive electrode active material for aqueous redox flow batteries provided in the present invention may be para-aminophenol represented by the following Formula 2, or nitrophenol represented by the following Formula 3. The compound of the following Formula 2 or 3 is in a redox state as shown herein, and may be applied under an aqueous electrolyte environment in an aqueous solution state because the compound has a characteristic of being highly soluble in water.

(11) ##STR00003##

(12) As described above, the compound represented by Formula 1 (including the compounds of Formulas 2 and 3) used as the positive electrode active material may be used at a concentration of 0.01 to 5 M, more preferably a concentration of 0.1 to 2 M in the electrolyte. When the compound is used within this range, excellent energy efficiency may be achieved.

(13) According to the present invention, the positive electrode electrolyte includes the aforementioned positive electrode active material and an aqueous solvent. An aqueous solution including at least one selected from sulfate ions (SO.sub.4.sup.2−), phosphate ions (PO.sub.4.sup.3−), and nitrate ions (NO.sub.3.sup.−) may be suitably used as the aqueous solvent. Such aqueous acid solutions may have a plurality of effects of promoting improvement of stability or reactivity of the positive electrode active material ions in the electrolyte and improvements of solubility, reducing internal resistance of the battery due to high ionic conductivity, and preventing generation of chlorine gas (Cl.sub.2) unlike the use of hydrochloric acid (HCl). Preferably, the aqueous solvent includes one or more selected from the group consisting of H.sub.2SO.sub.4, K.sub.2SO.sub.4, Na.sub.2SO.sub.4, H.sub.3PO.sub.4, H.sub.4P.sub.2O.sub.7, K.sub.2HPO.sub.4, Na.sub.3PO.sub.4, K.sub.3PO.sub.4, HNO.sub.3, KNO.sub.3, NaNO.sub.3, and a combination thereof.

(14) According to one exemplary embodiment of the present invention, the solvent used in the positive electrode electrolyte and the negative electrode electrolyte may be in the form of an aqueous H.sub.2SO.sub.4 solution. When an aqueous sulfuric acid (H.sub.2SO.sub.4) solution is used as the solvent for the electrolyte as described above, improvements of stability and reactivity of the positive electrode active material, a decrease in internal resistance, and the like may be promoted, as described above. In this case, when the concentration of sulfuric acid is excessively high, the presence of sulfate ions may cause a decline in solubility of the positive electrode active material or an increase in viscosity of the electrolyte. Therefore, the concentration of sulfuric acid is preferably less than or equal to 5 M, more preferably in a range of 1 to 3 M.

(15) As described above, when the positive and negative electrode electrolytes of the redox flow battery include the aforementioned electrolyte according to the present invention, the redox flow battery has no problems regarding metal deposition because the organic compound represented by Formula 1 is used as the active material, and may also be useful in realizing a high energy density because the active material may be used at high concentration due to an increase in solubility in the solvent, and attaining a high working voltage when the active material is applied to redox flow batteries.

(16) Also, the present invention provides a redox flow battery which is charged/discharged, which includes: a positive electrode cell including a positive electrode and a positive electrode electrolyte; a negative electrode cell including a negative electrode and a negative electrode electrolyte; an ion exchange membrane disposed between the positive electrode cell and the negative electrode cell; and a positive electrode electrolyte tank configured to supply a positive electrode electrolyte to the positive electrode cell by driving a pump and having a positive electrode electrolyte stored therein and a negative electrode electrolyte tank configured to supply a negative electrode electrolyte to the negative electrode cell by driving a pump and having a negative electrode electrolyte stored therein.

(17) In this case, each of the positive electrode electrolyte and the negative electrode electrolyte includes an electrode active material and an aqueous solvent. Here, the positive electrode active material included in the positive electrode electrolyte is the compound represented by Formula 1.

(18) Also, the negative electrode electrolyte may contain positive bivalent vanadium ions (V.sup.2+) and positive trivalent vanadium ions (V.sup.3+). To generate such vanadium ions, the negative electrode electrolyte may include a vanadium salt, and the vanadium salt is not particularly limited as long as the vanadium salt can release vanadium ions. For example, the vanadium salt may include vanadium sulfate, vanadium acetylacetonate, vanadium oxide sulfate hydrate, vanadium oxytriethoxide, and vanadium oxyfluoride. Preferably, vanadium sulfate is used in consideration of solubility. For example, tetravalent positive ions (VO.sup.2+═V.sup.4+) of the electrolyte in which a vanadium salt such as vanadium sulfate (VOSO.sub.4) is dissolved may be electrically reduced into trivalent positive ions (V.sup.3+), which may be then used.

(19) According to the present invention, the negative electrode electrolyte includes the aforementioned vanadium salt and an aqueous solvent. For the same reason as in the aforementioned positive electrode electrolyte, the aqueous solvent preferably includes one or more selected from H.sub.2SO.sub.4, K.sub.2SO.sub.4, Na.sub.2SO.sub.4, H.sub.3PO.sub.4, H.sub.4P.sub.2O.sub.7, K.sub.2HPO.sub.4, Na.sub.3PO.sub.4, K.sub.3PO.sub.4, HNO.sub.3, KNO.sub.3, NaNO.sub.3, HCl, and a combination thereof.

(20) Ion exchange membranes used in the conventional redox flow batteries may be used as the ion exchange membrane without any limitation. For example, the ion exchange membrane may be a fluorine-based polymer, a partial fluorine-based polymer, or a hydrocarbon-based polymer. More specifically, the ion exchange membrane may be selected from a homocopolymer, an alternating copolymer, a random copolymer, a block copolymer, a multiblock copolymer or a grafting copolymer. In this case, these copolymers are composed of one or more polymers selected from the group consisting of a perfluorosulfonic acid-based polymer, a hydrocarbon-based polymer, an aromatic sulfone-based polymer, an aromatic ketone-based polymer, a polybenzimidazole-based polymer, a polystyrene-based polymer, a polyester-based polymer, a polyimide-based polymer, a polyvinylidene fluoride-based polymer, a polyethersulfone-based polymer, a polyphenylene sulfide-based polymer, a polyphenylene oxide-based polymer, a polyphosphagen-based polymer, a polyethylene naphthalate-based polymer, a polyester-based polymer, a doped polybenzimidazole-based polymer, a polyether ketone-based polymer, a polyphenyl quinoxaline-based polymer, a polysulfone-based polymer, a sulfonated polyarylene ether-based polymer, a sulfonated polyether ketone-based polymer, a sulfonated polyether ether ketone-based polymer, a sulfonated polyamide-based polymer, a sulfonated polyimide-based polymer, a sulfonated polyphosphagen-based polymer, a sulfonated polystyrene-based polymer, and a radiation-polymerized sulfonated low-density polyethylene-g-polystyrene-based polymer.

MODE FOR INVENTION

(21) Hereinafter, preferred exemplary embodiments of the present invention will be described in order to aid in understanding the present invention. However, it should be understood that the description proposed herein is just a preferable example for the purpose of illustrations only. Therefore, it will be apparent to those skilled in the art that various changes and modifications can be made to the exemplary embodiments of the present invention without departing from the scope of the present invention, so it should be understood that the present invention covers all such changes and modifications provided they are within the scope of the appended claims and their equivalents.

Preparative Example 1

(22) 0.4 M 4-aminophenol was dissolved in an aqueous 3.0 M H.sub.2SO.sub.4 solution to prepare a positive electrode electrolyte.

Experimental Example 1

(23) To check redox characteristics of the positive electrode electrolyte prepared in Example 1, cyclic voltammetry was carried out using glassy carbon, Ag/AgCl and a platinum (Pt) wire as a working electrode, a reference electrode, and a counter electrode, respectively. Current values measured at a working electrode when a voltage spanning from −0.6 to 1.2 V was applied to the working electrode with a varying scan rate of 50 to 200 mV/s were recorded. The results are shown in FIG. 1.

(24) Results

(25) Referring to FIG. 1, from the results evaluated by the cyclic voltammetry, it can be seen that an oxidation/reduction current peak value increases as the scan rate increases, and this was a 2e.sup.− reaction because two peaks were observed during a reduction process. These results suggested that a reversible redox reaction was possible in an acidic aqueous solution.

(26) Also, FIG. 2 is an image of the 4-aminophenol aqueous solution before and after the cyclic voltammetry test. It was confirmed that the aqueous solution turned into purple during charging.

Example 1

(27) Positive and negative electrodes were manufactured using carbon felt with a size of 5×5 cm.sup.2, a bipolar plate, and a gold current collector. In this case, Nafion 115 was used as the ion exchange membrane.

(28) The electrolyte prepared in Preparative Example 1 was used as the positive electrode electrolyte. For the negative electrode electrolyte, 1.0 M vanadium sulfate (VOSO.sub.4) was dissolved in an aqueous 3.0 M sulfuric acid solution (H.sub.2SO.sub.4) to prepare a tetravalent vanadium (VO.sup.2+) solution, and the solution was electrically reduced to form trivalent vanadium ions (V.sup.3+), which was then used.

(29) A redox flow battery was manufactured using the battery thus assembled, the negative electrode electrolyte, and the positive electrode electrolyte prepared in Example 1. In this case, the electrolyte was circulated at a rate of 25 cc/min using a pump.

Comparative Example 1

(30) A redox flow battery was manufactured in the same manner as in Example 1, except that the positive electrode electrolyte was prepared by dissolving 1.0 M VOSO.sub.4 in an aqueous 3.0 M H.sub.2SO.sub.4 solution, and trivalent vanadium ions (V.sup.3+) obtained by separating ions from the positive electrode electrolyte were used as the negative electrode electrolyte. Thereafter, the electrolyte was circulated.

Experimental Example 2

(31) To evaluate the charge/discharge characteristics of the redox flow battery manufactured in Example 1, the redox flow battery was charged and discharged at ±100 mA in a voltage range of 0.1 to 1.4 V, and charge/discharge voltages with time are shown in FIG. 3.

(32) Results

(33) FIG. 3 is a graph illustrating a change in voltage for 16.sup.th to 20.sup.th charge/discharge cycles from the beginning. It was revealed that the redox flow battery was rechargeable and re-dischargeable within the same period of time at the same voltage as previously even when the number of charge/discharge cycles increased. That is, it can be seen that the redox reaction of the electrolyte on surfaces of the electrodes was reversible. Therefore, it can be seen that the charge/discharge behaviors of the single cell using 4-aminophenol as the positive electrode electrolyte were determined, and a working voltage range of the single cell was confirmed.

Experimental Example 3

(34) Expression capacities and current efficiencies of the redox flow batteries manufactured in Example 1 and Comparative Example 1 were measured. The current efficiency is an index that represents a degree of reversibility of a battery as a ratio of the quantity of discharged charges to the quantity of charged charges, and means that the battery is stably charged and discharged without an irreversible change of a material so that the current efficiency reaches 100%. Therefore, the efficiency represents an important value evaluated for the battery, the value of which may indirectly represent the lifespan of the battery. Together with the expression capacities, the results are listed in Table 1 and shown in FIG. 4. In this case, the redox flow batteries of Example 1 and Comparative Example 1 were assembled to having the same materials and areas, but were driven in different working voltage ranges of 0.4 to 1.2 V and 0.8 to 1.7 V, respectively, due to a difference in electrolytes therebetween.

(35) TABLE-US-00001 TABLE 1 Current efficiency (60.sup.th cycle, %) Measured once Measured in duplicate Example 1 91.6 93.1 Comparative Example 1 96.2 97.0

(36) Results

(37) As can be seen from the results of Table 1 and FIG. 4, it was revealed that the current efficiencies of the redox flow battery of Example 1 were measured to be 91.6 and 93.1, which were compared to the current efficiencies (96.2 and 97.0) of the vanadium redox flow battery of Comparative Example 1. Therefore, it was confirmed that the positive electrode electrolyte of Example 1 can be replaced with the positive electrode electrolyte for conventional vanadium batteries.