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CN-122000401-A - Aqueous redox flow battery

CN122000401ACN 122000401 ACN122000401 ACN 122000401ACN-122000401-A

Abstract

The application provides a water-based redox flow battery, and belongs to the technical field of energy storage systems. The electrolyte comprises an anode electrolyte, a diaphragm and a cathode electrolyte, wherein HOTEMPO-SO 3 Na is used as an active substance in the anode electrolyte, and (3-chloro-2-hydroxypropyl) -trimethylammonium chloride-4, 4' -bipyridine is used as an active substance in the cathode electrolyte. According to the application, through the cooperation of the positive electrode electrolyte and the negative electrode electrolyte, HOTEMPO-SO 3 Na with excellent redox performance and stability performance and (3-chloro-2-hydroxypropyl) -trimethylammonium chloride-4, 4' -bipyridine undergo a reversible redox reaction, and in the aspect of electrochemical performance, the redox flow battery is endowed with excellent redox performance and stability performance, SO that the energy density and the cycle life of the battery are effectively improved, the synthesis flow of active substances of the positive electrode electrolyte and the negative electrode electrolyte is short, the synthesis method is simple, and the production cost and the maintenance cost of the redox flow battery are effectively reduced.

Inventors

  • SHEN YONGMIAO
  • ZHANG KAI
  • ZHAO FUGANG
  • LIN XIAOMAN
  • Lin Fakun

Assignees

  • 浙江理工大学嵊州创新研究院有限公司
  • 绍兴市锐依博新材料技术有限公司

Dates

Publication Date
20260508
Application Date
20260407

Claims (10)

  1. 1. A water-based redox flow battery comprises a positive electrode electrolyte, a diaphragm and a negative electrode electrolyte, and is characterized in that HOTEMPO-SO 3 Na is adopted as an active substance in the positive electrode electrolyte, and (3-chloro-2-hydroxypropyl) -trimethylammonium chloride-4, 4' -bipyridine is adopted as an active substance in the negative electrode electrolyte.
  2. 2. The aqueous redox flow battery of claim 1, wherein the active material of the positive electrode electrolyte is prepared by: Adding 4-epoxy-2, 2', 6' -tetramethylpiperidine into sodium bisulphite aqueous solution, stirring for reaction, filtering, collecting precipitate, and drying to obtain (4-hydroxy-2, 2', 6' -tetramethylpiperidine) -4-methanesulfonate; Step two, dissolving (4-hydroxy-2, 2', 6' -tetramethyl piperidine) -4-methanesulfonate in water, adding sodium bicarbonate and sodium tungstate, adding hydrogen peroxide into the obtained water solution in batches, stirring overnight, and separating to obtain HOTEMPO-SO 3 Na.
  3. 3. The aqueous redox flow battery of claim 2, wherein the equivalent ratio of 4-epoxy-2, 2', 6' -tetramethylpiperidine to sodium bisulfite aqueous solution is 1:1.2, (4-hydroxy-2, 2', 6' -tetramethylpiperidine) -4-methanesulfonate, sodium bicarbonate and sodium tungstate is 1:0.5:0.01, and the equivalent ratio of hydrogen peroxide to aqueous solution is 1:2.
  4. 4. The aqueous redox flow battery of claim 2, wherein in step one, the reaction is stirred at 80 ℃ for 6 hours and in step two, the reaction is stirred at 40 ℃ overnight.
  5. 5. The aqueous redox flow battery according to claim 1, wherein the active material of the negative electrode electrolyte is prepared by adding 4,4 '-bipyridine and (3-chloro-2-hydroxypropyl) -trimethylammonium chloride into a reaction kettle, reacting for 24 hours at 120 ℃, cooling overnight, sequentially adding ethanol and acetone into the reaction product, and filtering and collecting to obtain (3-chloro-2-hydroxypropyl) -trimethylammonium chloride-4, 4' -bipyridine.
  6. 6. The aqueous redox flow battery of claim 5, wherein the equivalent ratio of 4,4' -bipyridine to 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 1:3, and the volume ratio of the reaction product, ethanol and acetone is 1:9:10.
  7. 7. The aqueous redox flow battery of claim 1, wherein the concentration of the active material in the positive electrode electrolyte is 0.1-0.2 mol/L and the concentration of the active material in the negative electrode electrolyte is 0.05-0.1 mol/L.
  8. 8. The aqueous redox flow battery of claim 1, wherein said membrane is an anion exchange membrane.
  9. 9. The aqueous redox flow battery of any one of claims 1-8, wherein HOTEMPO-SO 3 Na is dissolved in aqueous potassium chloride to obtain an anode electrolyte, and (3-chloro-2-hydroxypropyl) -trimethylammonium chloride-4, 4' -bipyridine is dissolved in aqueous potassium chloride to obtain a cathode electrolyte, and the anode electrolyte, the cathode electrolyte and a diaphragm are assembled to obtain the flow battery.
  10. 10. The aqueous redox flow battery of claim 9, wherein the concentration of the aqueous potassium chloride solution is 2-4 mol/L.

Description

Aqueous redox flow battery Technical Field The application relates to a water system redox flow battery, and belongs to the technical field of energy storage systems. Background The core working principle of the flow battery is that the anode electrolyte and the cathode electrolyte which are mutually separated realize the liquid circulation flow through the electrolyte storage and supply unit, and the active substances dissolved in the electrolyte are subjected to reversible oxidation-reduction reaction in the pile unit of the battery, so that the mutual conversion between electric energy and chemical energy is finally realized. The structure and the working principle also enable the output power and the capacity design of the flow battery to be relatively independent. However, the traditional flow battery has a plurality of defects in the aspects of electrolyte composition, electrode material development and the like, and greatly limits the performance optimization and application expansion of the flow battery. Disclosure of Invention In view of the above, the present application provides an aqueous redox flow battery with low cost and excellent performance. Specifically, the application is realized by the following scheme: A water-based redox flow battery comprises a positive electrode electrolyte, a diaphragm, a negative electrode electrolyte and a supporting electrolyte, wherein HOTEMPO-SO 3 Na is used as an active substance in the positive electrode electrolyte, and (3-chloro-2-hydroxypropyl) -trimethylammonium chloride-4, 4' -bipyridine is used as an active substance in the negative electrode electrolyte, and the supporting electrolyte is a 2M potassium chloride solution. Further, as preferable: The active material of the positive electrode electrolyte is prepared by the following steps: Adding 4-epoxy-2, 2', 6' -tetramethylpiperidine into sodium bisulphite aqueous solution, stirring for reaction, filtering, collecting precipitate, and drying to obtain (4-hydroxy-2, 2', 6' -tetramethylpiperidine) -4-methanesulfonate; Dissolving (4-hydroxy-2, 2', 6' -tetramethylpiperidine) -4-methanesulfonate in water, adding sodium bicarbonate and sodium tungstate, adding hydrogen peroxide into the obtained water solution in batches, stirring overnight, and separating to obtain (4-hydroxy-2, 2', 6' -tetramethylpiperidine-1-oxygen free radical) -4-methanesulfonate, which is designated HOTEMPO-SO 3 Na. The equivalent ratio of the (4-hydroxy-2, 2', 6' -tetramethyl piperidine) -4-methanesulfonate, the sodium bicarbonate and the sodium tungstate is 1:0.5:0.01, and the equivalent ratio of the hydrogen peroxide to the aqueous solution is 1:2. In the first step, the first step is to perform, The equivalent ratio of the 4-epoxy-2, 2', 6' -tetramethylpiperidine added to the aqueous solution of sodium bisulfite is 1:1.2. The stirring reaction refers to stirring reaction at 80 ℃ for 6 hours. In the second step, the second step is to carry out the process, The equivalent ratio of the (4-hydroxy-2, 2', 6' -tetramethyl piperidine) -4-methanesulfonate to the sodium bicarbonate to the sodium tungstate is 1:0.5:0.01, and the equivalent ratio of the hydrogen peroxide to the aqueous solution is 1:2. The stirring overnight was at 40 ℃ overnight. The active materials of the negative electrode electrolyte are prepared by adding 4,4 '-bipyridine and (3-chloro-2-hydroxypropyl) -trimethyl ammonium chloride into a reaction kettle, reacting for 24 hours at 120 ℃, cooling overnight, sequentially adding ethanol and acetone into the reaction product, filtering and collecting the reaction product, and obtaining (3-chloro-2-hydroxypropyl) -trimethyl ammonium chloride-4, 4' -bipyridine, which is marked as Dex-vi. More preferably: The equivalent ratio of the 4,4' -bipyridine to the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 1:3. The volume ratio of the reaction product to the ethanol to the acetone is 1:9:10. The concentration of the active material in the positive electrode electrolyte is 0.1-0.2 mol/L, and preferably 0.1 mol/L. The concentration of the active material in the negative electrode electrolyte is 0.05-0.1 mol/L, and preferably 0.05 mol/L. The assembly process of the water-based redox flow battery comprises the steps of dissolving HOTEMPO-SO 3 Na in a potassium chloride aqueous solution to obtain an anode electrolyte, dissolving (3-chloro-2-hydroxypropyl) -trimethylammonium chloride-4, 4' -bipyridine in the potassium chloride aqueous solution to obtain a cathode electrolyte, and sequentially assembling the anode electrolyte, the cathode electrolyte and a galvanic pile unit to obtain the flow battery. More preferably, the concentration of the potassium chloride aqueous solution is 2-4 mol/L. The cell stack is mainly composed of polar plates, current collectors and a diaphragm, wherein the diaphragm is an anion exchange membrane, such as a Nature diaphragm. The positive electrode electrolyte and the negative electrode electrolyt