CN114824398B - Polyacrylic acid grafted polymer flow battery system - Google Patents

Polyacrylic acid grafted polymer flow battery system Download PDF

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CN114824398B
CN114824398B CN202210336021.5A CN202210336021A CN114824398B CN 114824398 B CN114824398 B CN 114824398B CN 202210336021 A CN202210336021 A CN 202210336021A CN 114824398 B CN114824398 B CN 114824398B
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flow battery
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polyacrylic acid
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CN114824398A (en
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武奕
徐俊辉
王慧
姚圣鑫
李悦
陈留平
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China Salt Jintan Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention discloses a polyacrylic acid grafted polymer flow battery system. The polymer flow battery system comprises a positive electrode active material and a negative electrode active material, wherein the positive electrode active material is a PAA grafted TEMPO polymer, and the negative electrode active material is a PAA branch viologen polymer. The positive electrode active material and the negative electrode active material are organic polymers, and the polymers with linear structures are used for replacing small molecular active materials, so that more economical dialysis membranes and microporous materials sensitive to the scale can be used, and the cost of selectively penetrating the membranes is greatly reduced; compared with small molecular active substances, the polymer has good stability and can effectively prevent cross contamination among ions. Therefore, the PAA grafted TEMPO polymer and the viologen polymer are designed and prepared to obtain the organic polymer redox flow battery with the outstanding advantages of strong stability, good safety, flexible configuration, high response speed, green environmental protection and the like, and the organic polymer redox flow battery provides a powerful support for the application of large-scale electrochemical energy storage technology.

Description

Polyacrylic acid grafted polymer flow battery system
Technical Field
The invention relates to the technical field of flow batteries, in particular to a polyacrylic acid graft polymer flow battery system.
Background
Due to the gradual exhaustion of fossil energy and the environmental problems brought by the fossil energy, the development of new energy power generation has great significance. Wind energy and solar energy are most widely utilized at present, but the wind energy and the solar energy have discontinuity, the generated energy in different periods has larger difference, and huge tests are caused on the existing power grid. To address this peak-to-valley difference, it is also desirable to find low cost electrical energy storage systems. Flow battery technology is a hot spot for research of energy storage equipment due to higher cycle efficiency and stronger designability. The current commercial flow battery uses inorganic materials as active substances, however, the disadvantages of high cost, limited toxicity and resources, dendrite formation, low electrochemical activity and the like of the inorganic materials limit the large-scale application of the flow battery. The traditional flow battery made of inorganic materials has the defects of poor stability, low energy efficiency, environmental pollution and the like.
Disclosure of Invention
The invention aims to solve the technical problems that: the defects in the prior art are overcome, and the PAA grafted TEMPO polymer and the viologen polymer with linear structures are provided, so that the stability of the flow battery is greatly enhanced, and cross contamination among ions is effectively prevented; meanwhile, the macromolecular polymer is introduced, so that a dialysis membrane and a microporous material which are more economical and sensitive to the scale can be used, and the cost of the flow battery is greatly reduced; meanwhile, the polymer is used as a redox couple, has excellent electrochemical activity, and the obtained organic polymer redox flow battery has the outstanding advantages of strong stability, good safety, flexible configuration, high response speed, green environmental protection and the like, and provides a powerful support for the application of large-scale electrochemical energy storage technology.
The technical scheme adopted for solving the technical problems is as follows: a polyacrylic acid grafted polymer flow battery system comprises a positive electrode active material and a negative electrode active material, wherein the positive electrode active material is a PAA (polyacrylic acid) grafted TEMPO (2, 6-tetramethyl piperidine oxynitride) polymer, and the negative electrode active material is a PAA (polyacrylic acid) grafted viologen polymer;
the chemical structural formula of the PAA grafted TEMPO polymer is as follows:
the PAA grafted viologen polymer has a chemical structural formula as follows:
according to the polyacrylic acid grafted polymer redox flow battery system, PAA grafted viologen and PAA grafted TEMPO polymer with excellent electrochemical activity are designed and introduced to serve as redox couples, wherein the PAA grafted TEMPO polymer is a positive electrode active substance, the PAA grafted viologen polymer is a negative electrode active substance, the positive electrode active substance and the negative electrode active substance are organic polymers, the organic polymers have the advantages of low cost, easiness in synthesis and the like, and on the premise of not reducing the energy density, a more economic dialysis membrane or porous material can be used to effectively prevent cross contamination among ions, so that the organic polymer redox flow battery with high safety performance, high energy density, stable charge-discharge performance and high active material solubility is obtained.
Further, the PAA grafted TEMPO polymer is prepared by the following preparation method:
firstly, acrylic acid is taken as a monomer, an initiator is added, and polyacrylic acid is prepared by a free radical polymerization method; reintroduction of active molecules NH 2 -TEMPO, under the action of a catalyst, obtaining a functionalized APP grafted TEMPO polymer; the chemical reaction formula is shown as formula (1) and formula (2):
further, the PAA grafted viologen polymer is prepared by the following preparation method:
1, 3-propane sultone and 4,4' -bipyridine are taken as raw materials, SPy containing negative active molecules is synthesized through a Menschutkin reaction, and then the SPy is reacted with hydroxylamine sulfonic acid to synthesize an asymmetric viologen derivative NSPy; in the presence of a catalyst, NSPy containing a negative electrode active molecule is grafted in polyacrylic acid, so that the functionalized PAA grafted viologen polymer can be obtained, and the chemical reaction formulas of the functional PAA grafted viologen polymer are shown as formula (3), formula (4), formula (5) and formula (6):
further, the initiator is one or more of alpha-ketoglutaric acid, benzophenone and fluorescein.
Further, the catalyst is 4- (4, 6-dimethoxy triazin-2-yl) -4-methylmorpholine hydrochloride.
Further, the polyacrylic acid graft polymer flow battery system also comprises an anode liquid storage tank, a cathode liquid storage tank and a flow battery stack, wherein two ends of the flow battery stack are respectively communicated with the anode liquid storage tank and the cathode liquid storage tank; the positive electrode liquid storage reservoir and the negative electrode liquid storage reservoir are respectively liquid storage tanks for storing electrolyte or salt caves with physical solution cavities formed after salt mine exploitation;
the flow battery stack comprises a battery diaphragm, the battery diaphragm divides the flow battery stack into a positive electrode area and a negative electrode area, a positive electrode plate is arranged in the positive electrode area, a negative electrode plate is arranged in the negative electrode area, the positive electrode area is communicated with a positive electrode liquid storage tank through a positive electrode circulation pipeline, and the negative electrode area is communicated with a negative electrode liquid storage tank through a negative electrode circulation pipeline; the positive electrolyte in the positive electrode liquid storage tank consists of a positive electrode active material and a supporting electrolyte, and the negative electrolyte in the negative electrode liquid storage tank consists of a negative electrode active material and a supporting electrolyte; the battery separator is capable of supporting electrolyte penetration, preventing penetration of positive and negative electrode active materials.
Further, the molar concentration of the positive electrode active material in the positive electrode electrolyte is 0.1mol/L to 3.0mol/L, and the molar concentration of the supporting electrolyte is 0.1mol/L to 8.0mol/L.
Further, the molar concentration of the negative electrode active material in the negative electrode electrolyte is 0.1mol/L to 3.0mol/L, and the molar concentration of the supporting electrolyte is 0.1mol/L to 8.0mol/L.
Further, the polyacrylic acid graft polymer flow battery system also comprises current collectors which are respectively arranged at two sides of the flow battery stack, and the current collectors can collect current generated by active substances of the flow battery stack and conduct the current to an external component through wires.
Further, the current collector is a conductive metal plate, a graphite plate or a carbon-plastic composite plate.
The beneficial effects of the invention are as follows: the invention has the advantages of simple structure, reasonable design, simple and convenient operation, and the invention has the following advantages:
(1) PAA grafted viologen and TEMPO polymer with excellent electrochemical activity are introduced as redox couple, wherein the PAA grafted TEMPO polymer is an anode active substance, the PAA grafted viologen polymer is a cathode active substance, the anode active substance and the cathode active substance are organic polymers, and the polymers with linear structures are adopted to replace small molecular active substances, so that the organic polymers have the advantages of low cost, easiness in synthesis and the like; on the premise of not reducing the energy density, a more economic dialysis membrane or a porous material can be used for effectively preventing cross contamination among ions, so that the organic polymer redox flow battery with high safety performance, high energy density, stable charge and discharge performance and high solubility of an active material is obtained, and the cost of selectively permeating the membrane is greatly reduced;
(2) According to the invention, through the TEMPO polymer grafted by PAA and the viologen polymer, the organic polymer redox flow battery with the outstanding advantages of strong stability, good safety, flexible configuration, high response speed, green environmental protection and the like is obtained, and a powerful support is provided for the application of a large-scale electrochemical energy storage technology, so that the polymer flow battery system can solve the problem of large-scale electrochemical energy storage and fully utilizes some abandoned salt cavern resources.
Drawings
The invention will be further described with reference to the drawings and examples.
FIG. 1 is a schematic diagram of a polyacrylic acid graft polymer flow battery system according to the present invention;
FIG. 2 is a nuclear magnetic resonance plot of the PAA grafted TEMPO polymer of example 1 in D2O solvent, delta 7.31 and delta 6.97 being peaks after phenylhydrazine quenches free radicals, delta 1.25 being peaks of four methyl groups of NH2-TEMPO, delta 1.60 and delta 2.04 being peaks of methine and methylene groups, respectively, on the backbone, from the integration of the peaks, NH2-TEMPO: aa=1:6;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of NSPy of example 2 in D2O solvent;
FIG. 4 is a nuclear magnetic resonance plot of the PAA grafted viologen polymer of example 2 in D2O solvent;
FIG. 5 is a CV plot of PAA grafted TEMPO polymer solution (at a concentration of 1mg/mL in aqueous sodium chloride at pH=7) at a scan rate of 0.5V/s;
FIG. 6 is a CV plot of PAA grafted viologen polymer solution (at a concentration of 1mM in aqueous sodium chloride at pH=7) at a scan rate of 0.5V/s;
FIG. 7 is a graph of the cycling stability of PAA grafted TEMPO polymer-viologen polymer.
In the figure: 10. positive electrolyte reservoir, 20, flow battery stack, 21, negative electrode plate, 22, positive electrode plate, 23, current collector, 24, battery diaphragm, 25, positive circulation line, 26, negative circulation line, 30, negative electrolyte reservoir, 100, polyacrylic acid graft polymer flow battery system.
Detailed Description
The invention will now be described in further detail with reference to the drawings and a preferred embodiment. The drawings are simplified schematic representations which merely illustrate the basic structure of the invention and therefore show only the structures which are relevant to the invention.
The polyacrylic acid grafted polymer flow battery system 100 comprises a positive electrode active material and a negative electrode active material, wherein the positive electrode active material is a PAA grafted TEMPO polymer, and the negative electrode active material is a PAA grafted viologen polymer; PAA grafted TEMPO is used as the main redox active site, and the sodium carboxylate groups on the polymer are utilized to increase the solubility of the polymer; PAA grafted viologen polymer is used as a main redox active site, and the sulfonic acid group connected on the polymer is utilized to increase the solubility of the polymer. The PAA grafted TEMPO polymer has a positive active group (TEMPO) and the PAA grafted Viologen polymer has a negative active group (virogen).
The chemical structural formula of the PAA grafted TEMPO polymer is as follows:
the PAA grafted viologen polymer has a chemical structural formula as follows:
wherein, the PAA grafted TEMPO polymer is prepared by the following preparation method:
s11, mixing acrylic acid and an initiator, adding N, N-dimethylformamide, stirring until the solid is completely dissolved, irradiating with ultraviolet light, placing the obtained mixture in a dialysis bag with a molecular weight cut-off of 200 for dialysis, and freeze-drying to obtain polyacrylic acid, wherein the chemical reaction formula is shown in a formula (1);
s12, polyacrylic acid is dissolved in water, NH2-TEMPO and DMT-MM are sequentially added, stirring reaction is carried out, after the reaction is finished, alkaline solution is added, the mixture is placed in a dialysis bag with the molecular weight cut-off of 200 for dialysis, and the orange flocculent APP grafted TEMPO polymer is obtained after freeze drying, wherein the chemical reaction formula of the orange flocculent APP grafted TEMPO polymer is shown as a formula (2);
the PAA grafted viologen polymer is prepared by the following preparation method:
s21, mixing acrylic acid and an initiator, adding N, N-dimethylformamide, stirring until the solid is completely dissolved, irradiating with ultraviolet light, placing the obtained mixture in a dialysis bag with a molecular weight cut-off of 200 for dialysis, and freeze-drying to obtain polyacrylic acid, wherein the chemical reaction formula is shown in a formula (3);
s22, dissolving 4, 4-bipyridine in an acetonitrile solvent, adding 1, 3-propane sultone, condensing and refluxing for reaction, cooling to room temperature after the reaction is finished, filtering, washing with acetonitrile, and drying to obtain a white solid Spy, wherein the chemical reaction formula is shown in a formula (4);
s23, dissolving hydroxylamine sulfonic acid in water, and dropwise adding an alkaline solution under stirring at room temperature to prepare a sodium hydroxylamine sulfonate solution; dissolving the Spy prepared in the last step in water, dropwise adding a hydroxylamine sodium sulfonate solution under stirring at room temperature, and carrying out reflux reaction after the adding is finished; after the reaction is finished, cooling the reaction liquid to room temperature, adding a proper amount of alkali for neutralization, adding methanol until no precipitate is separated out, carrying out suction filtration, acidifying the filtrate with an acid solution, precipitating with acetone, and filtering and drying to obtain a yellow solid NSPy, wherein the chemical reaction formula is shown in a formula (5);
s24, diluting the polyacrylic acid solution with water, sequentially adding NSPy and a catalyst, stirring at room temperature for reaction, adding a proper amount of alkali solution into the reaction solution after the reaction is finished, placing the reaction solution into a dialysis bag with a molecular weight cut-off of 200 for dialysis, and freeze-drying to obtain an APP grafted viologen polymer, wherein the chemical reaction formula is shown in a formula (6);
in the preparation method of the PAA grafted TEMPO polymer and the PAA grafted viologen polymer, the initiator is one or more of alpha-ketoglutaric acid, diphenyl ketone and fluorescein; the catalyst is 4- (4, 6-dimethoxy triazine-2-yl) -4-methyl morpholine hydrochloride (DMT-MM).
The polyacrylic acid graft polymer flow battery system 100 further comprises a positive electrode liquid storage 10, a negative electrode liquid storage 30 and a flow battery stack 20, wherein two ends of the flow battery stack 20 are respectively communicated with the positive electrode liquid storage 10 and the negative electrode liquid storage 30; the positive electrode liquid storage 10 and the negative electrode liquid storage 30 are respectively liquid storage tanks for storing electrolyte or salt caves with physical solution cavities formed after salt mine exploitation;
the flow battery stack 20 comprises a battery diaphragm 24, the battery diaphragm 24 divides the flow battery stack 20 into a positive electrode area and a negative electrode area, a positive electrode plate 22 is arranged in the positive electrode area, a negative electrode plate 21 is arranged in the negative electrode area, the positive electrode area is communicated with the positive electrode liquid storage 10 through a positive electrode circulation pipeline 25, and the negative electrode area is communicated with a negative electrode liquid storage 30 through a negative electrode circulation pipeline 26; the positive electrode electrolyte in the positive electrode reservoir 10 is composed of a positive electrode active material and a supporting electrolyte, and the negative electrode electrolyte in the negative electrode reservoir 30 is composed of a negative electrode active material and a supporting electrolyte; the battery separator 24 is capable of supporting electrolyte penetration, preventing penetration of the positive and negative electrode active materials. The positive electrode circulation line 25 has a circulation pump for transporting the positive electrode electrolyte in the positive electrode reservoir 10 to the positive electrode region, and the negative electrode circulation line 26 has a circulation pump for transporting the negative electrode electrolyte in the negative electrode reservoir 30 to the negative electrode region.
The molar concentration of the positive electrode active material in the positive electrode electrolyte is 0.1 mol/L-3.0 mol/L, and the molar concentration of the supporting electrolyte is 0.1 mol/L-8.0 mol/L; the molar concentration of the negative electrode active material in the negative electrode electrolyte is 0.1mol/L to 3.0mol/L, and the molar concentration of the supporting electrolyte is 0.1mol/L to 8.0mol/L.
The positive electrode liquid storage 10 and the negative electrode liquid storage 30 are respectively pressurized sealed containers with the pressure of 0.1-0.5 MPa, inert gas is respectively introduced into the positive electrode liquid storage 10 and the negative electrode liquid storage 30 for purging and maintaining the pressure, and the inert gas is nitrogen or argon.
The battery separator 24 is an anion exchange membrane, a cation exchange membrane or a polymer porous membrane, and the pore diameter of the polymer porous membrane is 10 nm-300 nm.
The supporting electrolytes in the positive electrode liquid storage tank 10 and the negative electrode liquid storage tank 30 are NaCl salt solution, KCl salt solution and Na 2 SO 4 Salt solution, K 2 SO 4 Salt solution, mgCl 2 Salt solution, mgSO 4 Salt solution and CaCl 2 Salt solution, NH 4 At least one of the Cl salt solutions.
The positive electrode plate 22 and the negative electrode plate 21 are both carbon material electrodes, and the carbon material electrodes are one or a plurality of carbon felt, carbon paper, carbon cloth, carbon black, activated carbon fiber, activated carbon particles, graphene, graphite felt and glass carbon material.
The polyacrylic acid graft polymer flow battery system 100 further comprises current collectors 23, wherein the current collectors 23 are respectively arranged at two sides of the flow battery stack 20, and the current collectors 23 can collect current generated by active substances of the flow battery stack and conduct the current to external components, such as solar panels or wind driven generators, through wires.
The current collector 23 is a conductive metal plate, a graphite plate, or a carbon-plastic composite plate, and the conductive metal plate contains at least one metal of copper, nickel, and aluminum.
The polyacrylic acid graft polymer flow battery system 100 can be suitable for a battery environment of a salt cavity system (electrolyte generated in situ is utilized), and has the advantages of low cost, easy preparation of active materials, high safety performance, high energy density, stable charge and discharge performance, high solubility of the active materials and the like. Polymer flow battery system 100 is described in detail below in connection with particular embodiments.
In the cyclic voltammetry test of the electric pair, a CS series electrochemical workstation of Wuhan Kort company is adopted, a three-electrode system is used for testing the electrochemical performance of the electric pair, a working electrode is a glassy carbon electrode (Tianjin Aida Heng Cheng company), a reference electrode is an Ag/AgCl electrode, a counter electrode is a platinum electrode, and the scanning range of the positive electrode and the negative electrode electric pair is-1.0V respectively.
Example 1
PAA grafted TEMPO Polymer preparation
First, acrylic acid (4.32 g,60 mmol) and α -ketoglutaric acid (0.32 g,2.16 mmol) were added to a one-necked flask, and 50mL of N, N-dimethylformamide (hereinafter abbreviated as DMF) was further added thereto, followed by stirring at room temperature for 30 minutes until the solid was completely dissolved. And (3) irradiating for 30min by an ultraviolet lamp, dialyzing the reaction solution for 3 days by using a dialysis bag with a molecular weight cut-off (MWCO) of 200 after the reaction is finished, changing water every 8 hours or so, and freeze-drying to obtain the polyacrylic acid.
The polyacrylic acid (monomer 15 mmol) obtained by the above reaction was placed in a one-necked flask, and 20mL of water was added to dissolve the polyacrylic acid. Then sequentially adding 30mmol NH 2 Stirring and reacting TEMPO and 30mmol DMT-MM at room temperature for 72h, adding 4mL5M NaOH solution after the reaction, dialyzing the reaction solution with dialysis bag with molecular weight cut-off (MWCO) of 200 for 3 days, and changing water every 8h to obtain PAA jointThe branched TEMPO polymer solution was then freeze-dried to give an orange flocculent polymer.
Example 2
PAA grafted viologen polymer preparation
First, acrylic acid (4.32 g,60 mmol) and α -ketoglutaric acid (0.32 g,2.16 mmol) were added to a one-necked flask, and 50mL of N, N-dimethylformamide (hereinafter abbreviated as DMF) was further added thereto, followed by stirring at room temperature for 30 minutes until the solid was completely dissolved. And (3) irradiating for 30min by an ultraviolet lamp, dialyzing the reaction solution for 3 days by using a dialysis bag with a molecular weight cut-off (MWCO) of 200 after the reaction is finished, changing water every 8 hours or so, and freeze-drying to obtain the polyacrylic acid.
4, 4-bipyridine (2.5 g,16 mmol) and 1, 3-propane sultone (1.95 g,16 mmol) were added to a single-necked flask, and the mixture was dissolved in 25mL of acetonitrile, followed by stirring at 80℃for 24 hours. And after the reaction is finished, cooling to room temperature, carrying out suction filtration, repeatedly washing with acetonitrile for three times, and carrying out vacuum drying to obtain white solid SPy.
In a 100mL beaker, hydroxylamine sulfonic acid (2.49 g,22 mmol) as a white solid and 10mL of cold water were added, and after the hydroxylamine sulfonic acid was dissolved, 4.4mL of a 5M NaOH solution was added dropwise at room temperature to prepare a sodium hydroxylamine sulfonate solution. A100 mL single-neck flask is added with the white solid Spy (5.57 g,12.2 mmol) prepared in the previous step and 30mL of water, the mixture is stirred until part of the white solid is dissolved, a hydroxylamine sodium sulfonate solution is dropwise added under stirring at room temperature, the temperature is raised until reflux reaction is carried out for 6h after the dropwise addition is finished, and the SPy solid is completely dissolved and gradually changes into yellow in color. After the reaction, the reaction mixture was cooled to room temperature, and Na was added 2 CO 3 (1.12 g,11 mmol) of sodium hydroxylamine sulfonate which is not reacted is neutralized, bubbles are generated, the color of the solution is deepened, 50mL of methanol is added until no precipitate is separated out, pumping filtration is carried out, the yellow filtrate is acidified by hydrochloric acid solution (solution prepared by adding 5.5mL of water into 2.75mL of concentrated hydrochloric acid), the color of the solution becomes gradually lighter, finally acetone is precipitated, and a yellow solid NSPy is obtained after filtration and drying;
polyacrylic acid solution (13 mL,15 mmol) is added into a 150mL beaker, 20mL of water is added for dilution, yellow solid NSPy (2.64 g,8 mmol) and white solid DMT-MM (2.21 g,8 mmol) are sequentially added, stirring reaction is carried out at room temperature for 72h, 4mL of 5M NaOH solution is added into the reaction solution after the reaction is finished, dialysis is carried out for 3 days by using a dialysis bag with the molecular weight cut-off (MWCO) of 200, water is changed every 8h, and the PAA grafted viologen polymer can be obtained after freeze drying.
Electrochemical performance detection
(1) The PAA grafted TEMPO polymer solution (1 mg/mL in aqueous sodium chloride at pH=7) was studied by Cyclic Voltammetry (CV), with a scanning rate of 0.5V/s, a number of scans of 10, and a scanning result in FIG. 5, from which FIG. 5 it is seen that the redox potential of the PAA grafted TEMPO polymer was 0.64V;
(2) The PAA grafted viologen polymer solution (concentration 1mM in sodium chloride aqueous solution at pH=7) was studied by Cyclic Voltammetry (CV), and the results of the scanning were shown in FIG. 6, and the oxidation-reduction potentials of the PAA grafted TEMPO polymer were-0.9V and-0.6V, respectively;
(3) 52mg/mL of PAA grafted viologen polymer suspension and 0.1M NaCl mixed solution are added into the left negative electrode area, 60PAA grafted TEMPO polymer suspension and 0.1M NaCl mixed solution is added into the right positive electrode area, a regenerated cellulose RC membrane (MWCO=1KD, 3.5×3×0.45 cm) of Shanghai biological engineering Co., ltd is adopted as a battery diaphragm 24, standing is firstly set for 5min during testing, constant current charging (current is 20mA, voltage is less than or equal to 1.7V) and constant current discharging (current is 20mA, voltage is less than or equal to 0.3V) is carried out for 50 times, and finally the testing is ended. The cycle stability diagram of the PAA grafted TEMPO polymer-viologen polymer is shown in fig. 7, the single cell has a Coulombic Efficiency (CE) of 99.84%, a Voltage Efficiency (VE) and an Energy Efficiency (EE) of 45% after 350 charge and discharge cycles, and the aqueous organic polymer flow battery has stable performance.
According to the polyacrylic acid grafted polymer flow battery system 100, through the device combining the positive electrode liquid storage 10, the negative electrode liquid storage 30 and the flow battery stack 20, the flow battery stack 20 adopts the device combining the negative electrode plate 21, the positive electrode plate 22, the battery diaphragm 24, the positive electrode circulating pipeline 25, the negative electrode circulating pipeline 26, the circulating pump and the current collector 23, and adopts the PAA grafted TEMPO polymer and the PAA grafted viologen polymer as active substances to serve as the positive electrode active substances and the negative electrode active substances respectively, and the polyacrylic acid grafted polymer flow battery system 100 can be suitable for a battery environment of a salt cavern system (by utilizing an electrolyte generated in situ), has the advantages of low cost, easiness in preparing an active material, high safety performance, high energy density, stable charging and discharging performance and high solubility of the active material, and can solve the problem of large-scale (megawatt/megawatt) electrochemical energy storage, and fully utilizes some abandoned salt cavern (ore) resources.
The foregoing description is merely illustrative of specific embodiments of the invention, and the invention is not limited to the details shown, since modifications and variations of the foregoing embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims (10)

1. A polyacrylic acid graft polymer flow battery system, characterized by: the positive electrode active material is a polyacrylic acid PAA grafted 2, 6-tetramethyl piperidine nitroxide TEMPO polymer, and the negative electrode active material is a PAA grafted viologen polymer;
the chemical structural formula of the PAA grafted TEMPO polymer is as follows:
the PAA grafted viologen polymer has a chemical structural formula as follows:
2. the polyacrylic acid graft polymer flow battery system of claim 1, wherein: the PAA grafted TEMPO polymer is prepared by the following preparation method:
firstly, acrylic acid is taken as a monomer, an initiator is added, and polyacrylic acid is prepared by a free radical polymerization method; reintroduction of active molecules NH 2 -TEMPO, under the action of a catalyst, obtaining a functionalized PAA grafted TEMPO polymer; the chemical reaction formula is shown as formula (1) and formula (2):
3. the polyacrylic acid graft polymer flow battery system of claim 1, wherein: the PAA grafted viologen polymer is prepared by the following preparation method:
1, 3-propane sultone and 4,4' -bipyridine are taken as raw materials, a sulfydryl-4, 4' -bipyridine salt Spy containing negative active molecules is synthesized through a Menschutkin reaction, and then the sulfydryl-4 ' -bipyridine salt Spy reacts with hydroxylamine sulfonic acid to synthesize an asymmetric viologen derivative 1-amino-1 ' - (3-sulfydryl-propyl) -4,4' -bipyridine salt NSPy; in the presence of a catalyst, NSPy containing a negative electrode active molecule is grafted in polyacrylic acid, so that the functionalized PAA grafted viologen polymer can be obtained, and the chemical reaction formulas of the functional PAA grafted viologen polymer are shown as formula (3), formula (4), formula (5) and formula (6):
4. the polyacrylic acid graft polymer flow battery system of claim 2 or 3, wherein: the initiator is one or more of alpha-ketoglutaric acid, diphenyl ketone and fluorescein.
5. The polyacrylic acid graft polymer flow battery system of claim 2 or 3, wherein: the catalyst is 4- (4, 6-dimethoxy triazine-2-yl) -4-methyl morpholine hydrochloride.
6. The polyacrylic acid graft polymer flow battery system of claim 1, wherein: the liquid flow battery comprises a liquid flow battery, a positive electrode liquid storage, a negative electrode liquid storage and a liquid flow battery stack, wherein two ends of the liquid flow battery stack are respectively communicated with the positive electrode liquid storage and the negative electrode liquid storage; the positive electrode liquid storage reservoir and the negative electrode liquid storage reservoir are respectively liquid storage tanks for storing electrolyte or salt caves with physical solution cavities formed after salt mine exploitation;
the flow battery stack comprises a battery diaphragm, the battery diaphragm divides the flow battery stack into a positive electrode area and a negative electrode area, a positive electrode plate is arranged in the positive electrode area, a negative electrode plate is arranged in the negative electrode area, the positive electrode area is communicated with a positive electrode liquid storage tank through a positive electrode circulation pipeline, and the negative electrode area is communicated with a negative electrode liquid storage tank through a negative electrode circulation pipeline; the positive electrolyte in the positive electrode liquid storage tank consists of a positive electrode active material and a supporting electrolyte, and the negative electrolyte in the negative electrode liquid storage tank consists of a negative electrode active material and a supporting electrolyte; the battery separator is capable of supporting electrolyte penetration, preventing penetration of positive and negative electrode active materials.
7. The polyacrylic acid graft polymer flow battery system of claim 6, wherein: the molar concentration of the positive electrode active material in the positive electrode electrolyte is 0.1 mol/L-3.0 mol/L, and the molar concentration of the supporting electrolyte is 0.1 mol/L-8.0 mol/L.
8. The polyacrylic acid graft polymer flow battery system of claim 6, wherein: the molar concentration of the negative electrode active material in the negative electrode electrolyte is 0.1 mol/L-3.0 mol/L, and the molar concentration of the supporting electrolyte is 0.1 mol/L-8.0 mol/L.
9. The polyacrylic acid graft polymer flow battery system of claim 6, wherein: the flow battery further comprises current collectors which are respectively arranged at two sides of the flow battery stack, and the current collectors can collect current generated by active substances of the flow battery stack and conduct the current to an external component through wires.
10. The polyacrylic acid graft polymer flow battery system of claim 9, wherein: the current collector is a conductive metal plate, a graphite plate or a carbon-plastic composite plate.
CN202210336021.5A 2022-03-31 2022-03-31 Polyacrylic acid grafted polymer flow battery system Active CN114824398B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111613823A (en) * 2020-06-18 2020-09-01 中盐金坛盐化有限责任公司 Polymer flow battery system
CN111628185A (en) * 2020-05-27 2020-09-04 西安交通大学 Pyrroline/alkyl nitrogen oxygen free radical compound water system organic flow battery
KR20210156361A (en) * 2020-06-17 2021-12-27 김재광 Organic Secondary Electrodes and Rechargeable Organic Batteries

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111628185A (en) * 2020-05-27 2020-09-04 西安交通大学 Pyrroline/alkyl nitrogen oxygen free radical compound water system organic flow battery
KR20210156361A (en) * 2020-06-17 2021-12-27 김재광 Organic Secondary Electrodes and Rechargeable Organic Batteries
CN111613823A (en) * 2020-06-18 2020-09-01 中盐金坛盐化有限责任公司 Polymer flow battery system

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