Use of quaternary ammonium salt-type anthraquinone-based active material and salt cavern organic aqueous redox flow battery

Abstract

The present invention relates to use of a quaternary ammonium salt-type anthraquinone-based active material, and a salt cavern organic aqueous redox flow battery. The quaternary ammonium salt-type anthraquinone-based active material is used as a negative active material in a salt cavern battery, and a quaternary ammonium salt group is introduced, which can improve the solubility of anthraquinone in a neutral sodium chloride solution, thereby increasing the energy density of the battery. Also, the material has a relatively good stability, without the need for charging and discharging under the protection of an inert gas environment.

Claims

1. An use of a quaternary ammonium salt-type anthraquinone-based active material, comprising: preparing the quaternary ammonium salt-type anthraquinone-based active material, wherein the quaternary ammonium salt-type anthraquinone-based active material is represented by following formula: ##STR00003## wherein R is —(CH.sub.2).sub.nN.sup.+(CH.sub.3).sub.3, n=2˜12, wherein a method for preparing the quaternary ammonium salt-type anthraquinone-based active material comprises the following steps: step S1: dissolving 1,8-dihydroxyanthraquinone, bromoalkyltrimethylammonium bromide, potassium carbonate and potassium iodide into N,N-dimethylformamide with stirring for a reaction to obtain a resultant; and step S2: performing a primary suction filtration on the resultant after the reaction is completed to obtain a filtrate, adding an excess amount of tetrabutylammonium chloride into the filtrate obtained from the primary suction filtration, followed by a secondary suction filtration, and drying to obtain a product; and using the quaternary ammonium salt-type anthraquinone-based active material to prepare a negative electrolyte solution of a salt cavern battery.

2. The use of the quaternary ammonium salt-type anthraquinone-based active material according to claim 1, wherein the bromoalkyltrimethylammonium bromide in the step S1 has an alkyl chain with n=2˜12.

3. The use of the quaternary ammonium salt-type anthraquinone-based active material according to claim 1, wherein a molar ratio of reactants of the 1,8-dihydroxyanthraquinone:bromoalkyltrimethylammonium bromide:potassium carbonate:potassium iodide:N,N-dimethylformamide in the step S1 is 1:2 to 5:2 to 8:0.01 to 0.1:10 to 100.

4. The use of the quaternary ammonium salt-type anthraquinone-based active material according to claim 1, wherein the reaction in the step S1 is performed at a reaction temperature of 100° C. to 200° C. for a reaction time of 10 h to 48 h.

5. The use of the quaternary ammonium salt-type anthraquinone-based active material according to claim 4, wherein in the step S2, the primary suction filtration is performed on the resultant which is cooled to room temperature after the reaction is completed, and then the secondary suction filtration is performed, followed by vacuum drying, to obtain the product.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The above and/or additional aspects and advantages of the present invention will become obvious and easy to understand from the description of the embodiments in conjunction with the following accompanying drawings, wherein:

(2) FIG. 1 shows a flowchart of a method for preparing a quaternary ammonium salt-type anthraquinone-based active material according to an embodiment of the present invention.

(3) FIG. 2 shows a cyclic voltammogram according to Embodiment 1 of the present invention.

(4) FIG. 3 shows a rotating disk electrode test according to Embodiment 1 of the present invention.

(5) FIG. 4 shows the calculation of the diffusion coefficient of the active material according to Embodiment 1 of the present invention.

(6) FIG. 5 shows the calculation of the charge transfer rate constant according to Embodiment 1 of the present invention.

(7) FIG. 6 shows a graph of the potential vs. pH value according to Embodiment 1 of the present invention.

(8) FIG. 7 shows a graph of the charge/discharge voltage vs. capacity according to Embodiment 1 of the present invention.

(9) FIG. 8 shows a graph of the battery efficiency vs. cycles according to Embodiment 1 of the present invention.

(10) FIG. 9 shows a graph of the solubility according to Embodiment 1 of the present invention.

DESCRIPTION OF THE EMBODIMENTS

(11) Embodiments of the present invention will be described below in detail. Examples of the embodiments are shown in the accompanying drawings, where the same or similar elements, or elements with the same or similar functions are represented by the same or similar reference numerals throughout. The embodiments described below with reference to the accompanying drawings are exemplary, and are only used to explain the present invention, and should not be construed as limiting the present invention.

(12) In the description of the present invention, it should be understood that the orientation or positional relationship indicated by the terms “center,” “longitudinal,” “transverse,” “length,” “width,” “thickness,” “upper,” “lower,” “front,” “rear,” “left,” “right,” “vertical,” “horizontal,” “top,” “bottom,” “inner,” “outer,” “clockwise,” “counterclockwise,” “axial,” “radial,” “circumferential” or the like is based on the orientation or positional relationship shown in the accompanying drawings, and is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the indicated device or element must have a specific orientation, or be configured and operated in a specific orientation, and therefore should not be understood as limiting the present invention. In addition, the features defined by “first” or “second” may explicitly or implicitly include one or more such features. In the description of the present invention, “a plurality of” means two or more, unless otherwise specified.

(13) In the description of the present invention, it should be noted that the terms “installation,” “in connection with” and “in connection to” should be understood in a broad sense, unless otherwise clearly specified and limited. For example, they may be fixed connection, detachable connection, or integral connection; or mechanical connection or electrical connection; or direct connection, or indirect connection through an intermediate medium, or internal communication between two elements. For those of ordinary skill in the art, the specific meaning of the above terms in the present invention can be understood under specific circumstances.

(14) Use of a quaternary ammonium salt-type anthraquinone-based active material and a salt cavern organic aqueous redox flow battery according to embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

(15) According to the use of the quaternary ammonium salt-type anthraquinone-based active material according to an embodiment of the present invention, the quaternary ammonium salt-type anthraquinone-based active material is used as a negative active material in a salt cavern battery.

(16) As shown in FIG. 1, in some particular embodiments of the present invention, a method for preparing the quaternary ammonium salt-type anthraquinone-based active material includes the following steps.

(17) Step S1: 1,8-dihydroxyanthraquinone, bromoalkyltrimethylammonium bromide, potassium carbonate and potassium iodide are dissolved into N,N-dimethylformamide (DMF) with stirring for a reaction to obtain a resultant.

(18) Optionally, the bromoalkyltrimethylammonium bromide (Br—(CH.sub.2)nN.sup.+(CH.sub.3).sub.3Br.sup.−) in the step S1 has an alkyl chain with n=1, 2, 3, . . . , 12.

(19) According to an embodiment of the present invention, a molar ratio of reactants of the 1,8-dihydroxyanthraquinone:bromoalkyltrimethylammonium bromide:potassium carbonate:potassium iodide:N,N-dimethylformamide in the step S1 is 1:2 to 5:2 to 8:0.01 to 0.1:10 to 100.

(20) In some particular embodiments of the present invention, the reaction in the step S1 is performed at a reaction temperature of 100° C. to 200° C. for a reaction time of 10 h to 48 h. That is, 1,8-dihydroxyanthraquinone, bromoalkyltrimethylammonium bromide, potassium carbonate, and potassium iodide are dissolved into N,N-dimethylformamide (DMF) at a predetermined ratio with stirring, and then heated to a predetermined temperature for the reaction.

(21) Step S2: A primary suction filtration is performed on the resultant after the reaction is completed to obtain a filtrate, and an excess amount of tetrabutylammonium chloride is added into the filtrate obtained from the primary suction filtration, followed by a secondary suction filtration, and drying to obtain the product.

(22) Optionally, in the step S2, the primary suction filtration is performed on the resultant which is cooled to room temperature after the reaction is completed, and then the secondary suction filtration is performed, followed by vacuum drying to obtain the product.

(23) Therefore, through the individual synthetic design of the active material, a quaternary ammonium salt group is introduced, which can improve the solubility of anthraquinone in a neutral sodium chloride solution, thereby increasing the energy density of the battery.

(24) The salt cavern organic aqueous redox flow battery according to an embodiment of the present invention includes an electrolyte solution tank, two electrode plates and a battery separator.

(25) Specifically, the electrolyte solution tank is filled with electrolyte solutions. The two electrode plates are provided in the electrolyte solution tank and arranged to face each other. The battery separator is located in the electrolyte solution tank and is configured to separate the electrolyte solution tank into an anode zone in communication with a first electrolyte solution reservoir and a cathode zone in communication with a second electrolyte solution reservoir. A first electrode plate of the two electrode plates is provided in the anode zone and a second electrode plate of the two electrode plates is provided in the cathode zone. The anode zone contains a positive electrolyte solution including a positive active material and the cathode zone contains a negative electrolyte solution including a negative active material. The battery separator is configured to prevent penetration of the positive active material and the negative active material, and the negative active material is the quaternary ammonium salt-type anthraquinone-based active material.

(26) When the quaternary ammonium salt-type anthraquinone-based active material is used as the negative active material for the salt cavern organic aqueous redox flow battery, the introduced quaternary ammonium salt can not only increase the solubility of the material in the aqueous phase, but also avoid the change in solubility caused by combining with Ca.sup.2+ or Mg.sup.2+ ions.

(27) The salt cavern organic aqueous redox flow battery may further include two current collector plates, and the two electrode plates are arranged opposite to the two current collector plates, respectively.

(28) Further, the positive active material is an organic active molecule.

(29) Optionally, the positive active material is selected from a group of bipyridine derivatives, ferrocene and derivatives thereof, and the like.

(30) According to an embodiment of the present invention, the positive active material and the negative active material each have a concentration of 0.01 to 4 mol/L.

(31) In some particular embodiments of the present invention, the electrolyte solutions include a supporting electrolyte, and the battery separator is configured to be penetrated by the supporting electrolyte.

(32) Further, the supporting electrolyte includes a single-component neutral salt aqueous solution or a mixed neutral salt aqueous solution.

(33) Optionally, the supporting electrolyte is at least one selected from a group consisting of a NaCl salt solution, a KCl salt solution, a Na.sub.2SO.sub.4 salt solution, a K.sub.2SO.sub.4 salt solution, a MgCl.sub.2 salt solution, a MgSO.sub.4 salt solution, a CaCl.sub.2 salt solution, a CaSO.sub.4 salt solution, a BaCl.sub.2 salt solution, and a BaSO.sub.4 salt solution, for example, a high-concentration sodium chloride salt solution.

(34) According to an embodiment of the present invention, the battery separator is one selected from a group consisting of an anion exchange membrane, a cation exchange membrane, a permselective membrane, an anion/cation composite exchange membrane, a dialysis membrane and a porous membrane.

(35) In some particular embodiments of the present invention, the salt cavern organic aqueous redox flow battery further includes two electrolyte solution reservoirs, circulation pipelines and circulating pumps. The two electrolyte solution reservoirs are the first electrolyte solution reservoir and the second electrolyte solution reservoir, the first electrolyte solution reservoir and the second electrolyte solution reservoir being filled with the positive electrolyte solution and the negative electrolyte solution, respectively. A first circulation pipeline of the circulation pipelines is configured to deliver the positive electrolyte solution in the first electrolyte solution reservoir into or out of the anode zone, and a second circulation pipeline of the circulation pipelines is configured to deliver the negative electrolyte solution in the second electrolyte solution reservoir into or out of the cathode zone. The circulating pumps are provided in the circulation pipelines, respectively, and are configured to respectively supply the electrolyte solutions in a circulation flow.

(36) Optionally, the salt cavern organic aqueous redox flow battery has salt caverns each with an underground depth of 100 to 2000 m, a physical volume of 50,000 to 500,000 m.sup.3, and a geothermal temperature of 25° C. to 70° C., and the salt caverns each have a solution-mined cavity with a diameter of 40 to 120 m and a height of 60 to 400 m.

(37) According to an embodiment of the present invention, the salt cavern organic aqueous redox flow battery further includes electrolyte solution outlet pipes and electrolyte solution inlet pipes. The electrolyte solution outlet pipes are provided at openings of the salt caverns, respectively, lower ends of the electrolyte solution outlet pipes extend below liquid levels of the electrolyte solutions in the salt caverns, respectively, and upper ends of the electrolyte solution outlet pipes are respectively connected to the circulation pipelines to deliver the electrolyte solutions out of the salt caverns through the electrolyte solution outlet pipes, respectively. The electrolyte solution inlet pipes are provided at the openings of the salt caverns, respectively, and sleeved in the electrolyte solution outlet pipes, respectively, lower ends of the electrolyte solution inlet pipes extend toward the electrolyte solutions in the salt caverns, respectively, and upper ends of the electrolyte solution inlet pipes are respectively connected to the circulation pipelines to deliver the electrolyte solutions in the two electrolyte solution reservoirs into the salt caverns, respectively.

(38) Further, the electrolyte solution outlet pipes and the electrolyte solution inlet pipes each have an inner diameter of 15 m to 60 cm, and an outer diameter of 20 m to 80 cm.

(39) According to the use of the salt cavern organic aqueous redox flow battery according to an embodiment of the present invention, the salt cavern organic aqueous redox flow battery can be used in large-scale energy storage power stations, for peak shaving, emergency power supply, or storage of electrical energy from variable renewable energy sources.

(40) The preparation of the quaternary ammonium salt-type anthraquinone-based active material and the salt cavern organic aqueous redox flow battery according to the embodiments of the present invention will be described in detail below in combination with the particular embodiments.

Embodiment 1

(41) Preparation of an Anthraquinone-Based Active Material

(42) 1,8-Dihydroxyanthraquinone, Br—(CH.sub.2).sub.3N.sup.+(CH.sub.3).sub.3Br.sup.−, potassium carbonate, and potassium iodide were dissolved into N,N-dimethylformamide (DMF) at a predetermined ratio with stirring, where a molar ratio of the reactants 1,8-dihydroxyanthraquinone:Br—(CH.sub.2).sub.3N.sup.+(CH.sub.3).sub.3Br.sup.−:potassium carbonate:potassium iodide:DMF was 1:3:5:0.05:50.

(43) These reactants were allowed to react at 140° C. for 24 h to obtain a resultant which was cooled to room temperature after the reaction was completed, and then was subjected to suction filtration to obtain a filtrate. An excess amount of tetrabutylammonium chloride was added into the filtrate obtained after the suction filtration, followed by suction filtration and vacuum drying to obtain the product.

(44) FIG. 2 to FIG. 9 show the characterization of electrochemical performances of the prepared active material. The prepared quaternary ammonium salt-type anthraquinone-based active material has a diffusion coefficient on a graphite felt electrode of 3.94×10.sup.−6 cm.sup.2/s and a charge transfer rate constant of 3.02×10.sup.−3 cm/s.

(45) The synthetic route of the prepared active material may be as shown in the following formula:

(46) ##STR00001##

(47) The redox mechanism is shown as follows:

(48) ##STR00002##

(49) Battery Performance Test

(50) Two salt caverns each with an underground depth of 600 m, a physical volume of 100,000 m.sup.3, a height of 80 m, a maximum diameter of 60 m, and a geothermal temperature of 30° C. were used as storage tanks for catholyte and anolyte, respectively, and the sleeve had an inner diameter of 20 cm and an outer diameter of 50 cm.

(51) 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxide (OH-TEMPO) at a concentration of 0.5 mol/L was employed as the anolyte, the quaternary ammonium salt-type anthraquinone-based active material synthesized above at a concentration of 0.5 mol/L was employed as the catholyte, and a 2 mol/L NaCl solution was employed as the supporting electrolyte solution. The electrolyte viscosity was about 10 mPas. Graphite felt electrodes were employed as the positive and negative electrodes, respectively, and a cation exchange membrane was employed as the battery separator. For a single battery stack, at the current density of 10 mA/cm.sup.2, the Coulombic efficiency was 99%, the voltage efficiency was 88%, and the energy efficiency was 88%.

Embodiment 2

(52) Preparation of an Anthraquinone-Based Active Material

(53) 1,8-Dihydroxyanthraquinone, Br—(CH.sub.2).sub.2N.sup.+(CH.sub.3).sub.3Br.sup.−, potassium carbonate and potassium iodide were dissolved into N,N-dimethylformamide (DMF) at a predetermined ratio with stirring, where a molar ratio of the reactants Br—(CH.sub.2).sub.2N.sup.+(CH.sub.3).sub.3Br:potassium carbonate:potassium iodide:DMF was 1:3:6:0.02:60.

(54) These reactants were allowed to react at 160° C. for 20 h to obtain a resultant which was cooled to room temperature after the reaction was completed, and then was subjected to suction filtration to obtain a filtrate. An excess amount of tetrabutylammonium chloride was added into the filtrate obtained after the suction filtration, followed by suction filtration and vacuum drying to obtain the product.

(55) Battery Performance Test

(56) Two salt caverns each with an underground depth of 900 m, a physical volume of 150,000 m.sup.3, a height of 120 m, a maximum diameter of 80 m, and a geothermal temperature of 37° C. were used as storage tanks for catholyte and anolyte, respectively, and the sleeve had an inner diameter of 30 cm and an outer diameter of 60 cm.

(57) A quaternary ammonium salt-type ferrocene at a concentration of 0.5 mol/L was employed as the anolyte, the quaternary ammonium salt-type anthraquinone-based active material synthesized above at a concentration of 0.5 mol/L was employed as the catholyte, and a 2 mol/L NaCl solution was employed as the supporting electrolyte solution. The electrolyte viscosity was about 10 mPas. Graphite felt electrodes were employed as the positive and negative electrodes, respectively, and a cation exchange membrane was employed as the battery separator. For a single battery stack, at the current density of 30 mA/cm.sup.2, the Coulombic efficiency was 99%, the voltage efficiency was 76%, and the energy efficiency was 75%.

Embodiment 3

(58) Preparation of an Anthraquinone-Based Active Material

(59) 1,8-Dihydroxyanthraquinone, Br—(CH.sub.2).sub.4N.sup.+(CH.sub.3).sub.3Br.sup.−, potassium carbonate and potassium iodide were dissolved into DMF at a predetermined ratio with stirring, where a molar ratio of the reactants Br—(CH.sub.2).sub.4N.sup.+(CH.sub.3).sub.3Br:potassium carbonate:potassium iodide:DMF was 1:3:5:0.02:80.

(60) These reactants were allowed to react at 180° C. for 18 h to obtain a resultant which was cooled to room temperature after the reaction was completed, and then was subjected to suction filtration to obtain a filtrate. An excess amount of tetrabutylammonium chloride was added into the filtrate obtained after the suction filtration, followed by suction filtration and vacuum drying to obtain the product.

(61) Battery Performance Test

(62) Two salt caverns each with an underground depth of 800 m, a physical volume of 120,000 m.sup.3, a height of 100 m, a maximum diameter of 80 m, and a geothermal temperature of 30° C. were used as storage tanks for catholyte and anolyte, respectively, and the sleeve had an inner diameter of 20 cm and an outer diameter of 50 cm.

(63) OH-TEMPO at a concentration of 0.3 mol/L was employed as the anolyte, the quaternary ammonium salt-type anthraquinone-based active material synthesized above at a concentration of 0.3 mol/L was employed as the catholyte, and a 1.5 mol/L NaCl solution was employed as the supporting electrolyte solution. The electrolyte viscosity was about 12 mPas. Graphite felt electrodes were employed as the positive and negative electrodes, respectively, and a cation exchange membrane was employed as the battery separator. For a single battery stack, at the current density of 30 mA/cm.sup.2, the Coulombic efficiency was 99%, the voltage efficiency was 76%, and the energy efficiency was 75%.

Embodiment 4

(64) Preparation of an Anthraquinone-Based Active Material

(65) 1,8-Dihydroxyanthraquinone, Br—(CH.sub.2).sub.6N.sup.+(CH.sub.3).sub.3Br.sup.−, potassium carbonate and potassium iodide were dissolved into DMF at a predetermined ratio with stirring, where a molar ratio of the reactants Br—(CH.sub.2).sub.6N.sup.+(CH.sub.3).sub.3Br:potassium carbonate:potassium iodide:DMF was 1:4:7:0.02:65.

(66) These reactants were allowed to react at 180° C. for 18 h and was cooled to room temperature after the reaction was completed, and then was subjected to suction filtration to obtain a filtrate. An excess amount of tetrabutylammonium chloride was added into the filtrate obtained after the suction filtration, followed by suction filtration and vacuum drying to obtain the product.

(67) Battery Performance Test

(68) Two salt caverns each with an underground depth of 1000 m, a physical volume of 200,000 m.sup.3, a height of 140 m, a maximum diameter of 120 m, and a geothermal temperature of 30° C. were used as storage tanks for catholyte and anolyte, respectively, and the sleeve had an inner diameter of 20 cm and an outer diameter of 50 cm.

(69) OH-TEMPO at a concentration of 0.5 mol/L was employed as the anolyte, the quaternary ammonium salt-type anthraquinone-based active material synthesized above at a concentration of 0.5 mol/L was employed as the catholyte, and a 1.2 mol/L NaCl solution was employed as the supporting electrolyte solution. The electrolyte viscosity was about 15 mPas. Graphite felt electrodes were employed as the positive and negative electrodes, respectively, and a cation exchange membrane was employed as the battery separator. For a single battery stack, at the current density of 30 mA/cm.sup.2, the Coulombic efficiency was 99%, the voltage efficiency was 76%, and the energy efficiency was 75%.

(70) In summary, when abundant and low-cost anthraquinone-based active materials are used as the negative active material in the electrolyte solution, the introduction of a quaternary ammonium salt group can not only improve the solubility of anthraquinone in a neutral sodium chloride solution and increase the energy density of the battery, but also provide relatively good electrochemical redox properties. The material has a relatively good stability, so the battery does not need to be charged and discharged under the protection of an inert gas environment. The use of a natural salt cavern as an electrolyte solution reservoir has advantages of large capacity, low cost, safety and environmental friendliness, and it is suitable for large-scale energy storage power stations.

(71) In the description of this specification, the description with reference to the terms “an embodiment,” “some embodiments,” “an exemplary embodiment,” “an example,” “a particular example” or “some examples” and the like means that the specific features, structures, materials, or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the illustrative expression of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.

(72) Although the embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principle and purpose of the present invention. The scope of the present invention is defined by the claims and their equivalents.