CN108400365B - Zinc-bromine flow battery - Google Patents
Zinc-bromine flow battery Download PDFInfo
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- CN108400365B CN108400365B CN201810172461.5A CN201810172461A CN108400365B CN 108400365 B CN108400365 B CN 108400365B CN 201810172461 A CN201810172461 A CN 201810172461A CN 108400365 B CN108400365 B CN 108400365B
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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
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- 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
- Y02E60/10—Energy storage using batteries
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- 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
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Abstract
The invention discloses a zinc-bromine flow battery, which comprises a positive plate, a negative plate and a battery diaphragm arranged between the positive plate and the negative plate; the positive plate is preferably one of a graphite plate, a carbon felt, a graphite felt or a carbon cloth; the negative plate is preferably one of a graphite plate, a carbon felt, a graphite felt or a carbon cloth; the battery diaphragm is a single-layer PE, PP film, 3 layers of PP, PE film or polyacrylonitrile base film. The battery diaphragm of the zinc-bromine flow battery prepared by the invention has longitudinal tensile strength of more than 168MPa and thermal shrinkage of less than 1.2 percent, and has excellent mechanical properties. The zinc-bromine flow battery can be charged and discharged for a long time with large capacity, and the charging and discharging efficiency is high.
Description
Technical Field
The invention relates to a battery, in particular to a zinc-bromine flow battery.
Background
The zinc-bromine flow battery is a new electrochemical energy storage technology, and compared with other energy storage technologies, the zinc-bromine flow battery has the advantages of high energy conversion efficiency, flexible system design, large storage capacity, free site selection, deep discharge, safety, environmental protection, low maintenance cost and the like, and can be widely applied to the aspects of power generation and energy storage of renewable energy sources such as wind energy, solar energy and the like, peak clipping and valley filling of emergency power supply systems, backup power stations, power systems and the like.
The zinc-bromine flow battery is a flow energy storage battery. The diaphragm is an important component of the zinc-bromine flow battery and plays a role in blocking electrolyte of the positive electrode and the negative electrode and providing a proton transmission channel. The proton conductivity, chemical stability, ion selectivity and the like of the membrane directly influence the electrochemical performance and service life of the battery; it is desirable that the membranes have low active material permeability (i.e., high selectivity) and low sheet resistance (i.e., high ionic conductivity), while also having good chemical stability and low cost. The separator in the battery may affect the use efficiency of the battery. The cost of the electrolyte in the battery accounts for almost 30% of the total cost of the flow battery, so the price of the electrolyte determines the overall cost of the battery. The zinc-bromine flow battery has high energy density, low price and easy acquisition of a large amount of zinc, so the rechargeable battery containing a zinc system has strong competitiveness in a large-scale energy storage system. This electrolyte characteristic determines the great advantage of zinc-bromine flow batteries in terms of cost. When the zinc-bromine flow battery discharges, the metal zinc deposited on the surface can be completely dissolved in the electrolyte, so that the deep charge and discharge are frequently carried out without causing battery loss.
The following properties of the separator for the zinc-bromine flow battery need to be noted in the development and research. First, in the physical chemistry, the separator for zinc-bromine flow battery needs to have a small swelling ratio, ensure good mechanical strength, be uniform in all directions, have sufficient tensile tension, and also have certain flexibility and toughness to reduce problems in installation and facilitate assembly and disassembly. In the aspect of electrochemistry, the diaphragm needs to have higher conductivity and stronger ion selectivity, so that the battery efficiency can be effectively improved, the passing rate of the elemental bromine is reduced, the positive and negative electrolytes are better isolated, the self-discharge of the battery is prevented, and the service efficiency is improved. Finally, the separator must have high acid resistance, high oxidation resistance, and stable electrochemistry.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the technical problem to be solved by the present invention is to provide a zinc-bromine flow battery.
A zinc-bromine flow battery comprises a positive plate, a negative plate and a battery diaphragm arranged between the positive plate and the negative plate;
the positive plate is metal, such as Pb, Ti and the like; carbon such as graphite, carbon cloth, carbon felt, etc.; the positive plate is preferably one of a graphite plate, a carbon felt, a graphite felt or a carbon cloth;
the negative plate is metal, such as Pb, Ti and the like; carbon such as graphite, carbon cloth, carbon felt, etc.; the negative electrode plate is preferably one of a graphite plate, a carbon felt, a graphite felt or a carbon cloth;
the battery diaphragm is a composite material, such as a conductive polymer, a high-molecular composite material and the like, preferably a single-layer PE, PP film, 3-layer PP, PE film, Nafion film or polyacrylonitrile-based film, and preferably a polyacrylonitrile battery diaphragm.
A Nafion membrane, which is a perfluorosulfonic acid membrane, english name: nafion nr 50(beads10-35mesh), CAS number: 31175-20-9.
Further preferably, the polyacrylonitrile battery diaphragm is prepared by the following method:
s1, dissolving a high molecular polymer in an organic solvent to obtain a solution A with the high molecular polymer mass fraction of 10-15%;
s2, adding a stabilizer, polyacrylonitrile and polyvinylpyrrolidone into N, N-dimethylacetamide to obtain a solution B;
s3, blade-coating the solution B on a glass plate, and standing to form a film; dipping the film and the glass plate in a coagulating liquid; tearing off the film, washing and drying to obtain a polyacrylonitrile-based film;
s4, coating the solution A on a polyacrylonitrile-based membrane, and drying to obtain the polyacrylonitrile battery diaphragm.
Preferably, the polyacrylonitrile battery diaphragm is prepared by the following method:
s1, dissolving a high molecular polymer in an organic solvent to obtain a solution A with the high molecular polymer mass fraction of 10-15%;
the high molecular polymer is polybenzimidazole and/or perfluorosulfonic acid polymer; preferably, the polybenzimidazole accounts for 25-35 wt% of the high molecular polymer, and the perfluorosulfonic acid polymer accounts for 65-75 wt%. More preferably, the polybenzimidazole accounts for 30 wt% of the high molecular polymer, and the perfluorosulfonic acid polymer accounts for 70 wt%;
preferably, the organic solvent in step S1 is one of dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide;
s2, adding a stabilizer, polyacrylonitrile and polyvinylpyrrolidone into N, N-dimethylacetamide, stirring at the temperature of 60-80 ℃ for 20-30 h at the rotating speed of 300-500 r/min, and standing in a dark place for 20-30 h to obtain a solution B;
preferably, the mass ratio of the stabilizer to the polyacrylonitrile to the polyvinylpyrrolidone to the N, N-dimethylacetamide is (0.5-0.8): (10-15): (1-3): (70-85);
s3, uniformly blade-coating the solution B on a clean glass plate, and after blade-coating, standing for 5-10 min under the conditions that the temperature is 35-50 ℃ and the humidity is 70-90% to form a film; then immersing the film and the glass plate into a solidification solution for 60-80 s; tearing off the film, washing with water, and vacuum-drying at 60-80 ℃ for 4-8 h to obtain a polyacrylonitrile-based film;
the thickness of the polyacrylonitrile-based film is controlled to be 50-80 mu m;
s4, coating the solution A on a polyacrylonitrile base film, drying for 1.5-3 h at 50-70 ℃, soaking in 75-90 ℃ water for 10-15 h, and vacuum drying for 6-10 h at 40-60 ℃ to obtain the polyacrylonitrile battery diaphragm; the dosage of the solution A is 40-60 mu L of solution A coated on each square centimeter of polyacrylonitrile-based film.
Preferably, in the step S3, the condensed liquid is prepared from N, N-dimethylacetamide and water in a volume ratio of (2-5): 20 are mixed together.
At present, a common battery diaphragm in the prior art is a polymer film, and a simple polymer film has poor thermal stability and low mechanical strength, and is easy to swell after long-term use to reduce the service efficiency of a battery. According to the invention, the stabilizer is added into the polymer film, so that the prepared diaphragm has more abundant pores and better mechanical strength, has excellent conductivity, and can be used for a long time without damage.
Preferably, the stabilizer is montmorillonite and/or silica.
Further preferably, the stabilizer is organic montmorillonite and/or silica.
As one preferable scheme, the stabilizer is organic montmorillonite and silicon dioxide according to the mass ratio of (3-5): 1 are mixed.
Preferably, the preparation method of the organic montmorillonite comprises the following steps: dispersing 1-3 g of montmorillonite powder in 30-50 mL of water, and stirring at 45-60 ℃ and at a rotating speed of 300-500 r/min for 40-80 min to obtain montmorillonite dispersion liquid; adding 0.7-1.1 g of hexadecyl trimethyl ammonium bromide into 8-12 mL of water with the temperature of 80-90 ℃, and stirring at the rotating speed of 100-300 r/min for 5-10 min to obtain a hexadecyl trimethyl ammonium bromide aqueous solution; dropping hexadecyl trimethyl ammonium bromide aqueous solution into the montmorillonite dispersion liquid at the speed of 0.05-0.1 g/s under stirring at the rotating speed of 100-300 r/min, continuing stirring at the rotating speed of 100-300 r/min for 5-8 h after dropping, performing suction filtration, washing the obtained solid with water until no bromide ion is contained, performing vacuum drying on the obtained solid at the temperature of 70-90 ℃ for 20-30 h, and grinding into powder to obtain the organic montmorillonite.
The invention has the beneficial effects that:
the battery diaphragm of the zinc-bromine flow battery prepared by the invention has longitudinal tensile strength of more than 168MPa and thermal shrinkage of less than 1.2 percent, and has excellent mechanical properties. The zinc-bromine flow battery can be charged and discharged for a long time with large capacity, and the charging and discharging efficiency is high. Moreover, the battery diaphragm also has higher conductivity. The higher the conductivity, the lower the resistance, which means that the barrier ability of the separator to the flow of electrons is smaller, and the electrochemical performance of the separator is more excellent.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not intended to limit the scope of the invention, as various equivalent modifications of the invention will occur to those skilled in the art upon reading the present disclosure and fall within the scope of the appended claims.
Example 1
S1, dissolving a perfluorosulfonic acid polymer in N-methyl pyrrolidone to obtain a solution A with the perfluorosulfonic acid polymer mass fraction of 12%;
s2, adding a stabilizer, polyacrylonitrile and polyvinylpyrrolidone into N, N-dimethylacetamide, stirring at 70 ℃ for 24 hours at a rotating speed of 500r/min, and standing in the dark for 24 hours to eliminate bubbles to obtain a solution B; the mass ratio of the stabilizer to the polyacrylonitrile to the polyvinylpyrrolidone to the N, N-dimethylacetamide is 0.6: 14: 2: 84;
s3, uniformly coating the solution B on a clean glass plate, and after coating, exposing the glass plate to the conditions of 50 ℃ and 90% of humidity and standing for 10min to form a film; then, putting the film and the glass plate into a solidification liquid for soaking for 60s (ensuring that the solidification liquid can submerge the glass plate and the film); tearing off the film, washing with deionized water, and vacuum drying at 70 ℃ for 5h to obtain a polyacrylonitrile-based film; the thickness of the polyacrylonitrile-based film is controlled to be 70 mu m; the coagulating liquid is prepared from N, N-dimethylacetamide and deionized water according to a volume ratio of 3: 20 are mixed together.
S4, coating the solution A on a polyacrylonitrile-based membrane, drying for 2h at 60 ℃, soaking in deionized water at 80 ℃ for 12h, and vacuum drying at 40 ℃ for 10h to obtain a polyacrylonitrile battery diaphragm; the dosage of the solution A is 50 mu L of solution A coated on each square centimeter of polyacrylonitrile-based film.
The stabilizer is organic montmorillonite.
The preparation method of the organic montmorillonite comprises the following steps: dispersing 2g of montmorillonite powder in 40mL of water, and stirring at 50 ℃ and a rotating speed of 300r/min for 60min to obtain montmorillonite dispersion liquid; adding 0.8g of hexadecyl trimethyl ammonium bromide into 10mL of water with the temperature of 90 ℃ and stirring for 10min at the rotating speed of 200r/min to obtain a hexadecyl trimethyl ammonium bromide aqueous solution; dropping hexadecyl trimethyl ammonium bromide aqueous solution with the temperature of 90 ℃ into montmorillonite dispersion liquid with the temperature of 50 ℃ at the speed of 0.05g/s under stirring at the rotating speed of 300r/min, stirring for 6 hours at the rotating speed of 300r/min under water bath with the temperature of 50 ℃ after dropping is finished, performing suction filtration by using conventional filter paper, washing the obtained solid by deionized water until the solid does not contain bromide ions (detected by silver nitrate), drying the obtained solid for 24 hours at the temperature of 80 ℃ and the vacuum degree of 0.02MPa, and grinding into powder to obtain the organic montmorillonite.
Example 2
S1, dissolving polybenzimidazole in N-methyl pyrrolidone to obtain a solution A with the mass fraction of polybenzimidazole of 12%;
s2, adding a stabilizer, polyacrylonitrile and polyvinylpyrrolidone into N, N-dimethylacetamide, stirring at 70 ℃ for 24 hours at a rotating speed of 500r/min, and standing in the dark for 24 hours to eliminate bubbles to obtain a solution B; the mass ratio of the stabilizer to the polyacrylonitrile to the polyvinylpyrrolidone to the N, N-dimethylacetamide is 0.6: 14: 2: 84;
s3, uniformly coating the solution B on a clean glass plate, and after coating, exposing the glass plate to the conditions of 50 ℃ and 90% of humidity and standing for 10min to form a film; then, putting the membrane and the glass plate into a solidification liquid for soaking for 60s (ensuring that the solidification liquid can submerge the glass plate and the membrane); tearing off the film, washing with deionized water, and vacuum drying at 70 ℃ for 5h to obtain a polyacrylonitrile-based film; the thickness of the polyacrylonitrile-based film is controlled to be 70 mu m; the coagulating liquid is prepared from N, N-dimethylacetamide and deionized water according to a volume ratio of 3: 20 are mixed together.
S4, coating the solution A on a polyacrylonitrile-based membrane, drying for 2h at 60 ℃, soaking in deionized water at 80 ℃ for 12h, and vacuum drying at 40 ℃ for 10h to obtain a polyacrylonitrile battery diaphragm; the dosage of the solution A is 50 mu L of solution A coated on each square centimeter of polyacrylonitrile-based film.
The stabilizer is silicon dioxide.
Example 3
S1, dissolving a perfluorosulfonic acid polymer in N-methyl pyrrolidone to obtain a solution A with the perfluorosulfonic acid polymer mass fraction of 12%;
s2, adding a stabilizer, polyacrylonitrile and polyvinylpyrrolidone into N, N-dimethylacetamide, stirring at 70 ℃ for 24 hours at a rotating speed of 500r/min, and standing in the dark for 24 hours to eliminate bubbles to obtain a solution B; the mass ratio of the stabilizer to the polyacrylonitrile to the polyvinylpyrrolidone to the N, N-dimethylacetamide is 0.6: 14: 2: 84;
s3, uniformly coating the solution B on a clean glass plate, and after coating, exposing the glass plate to the conditions of 50 ℃ and 90% of humidity and standing for 10min to form a film; then, putting the film and the glass plate into a solidification liquid for soaking for 60s (ensuring that the solidification liquid can submerge the glass plate and the film); tearing off the film, washing with deionized water, and vacuum drying at 70 ℃ for 5h to obtain a polyacrylonitrile-based film; the thickness of the polyacrylonitrile-based film is controlled to be 70 mu m; the coagulating liquid is prepared from N, N-dimethylacetamide and deionized water according to a volume ratio of 3: 20 are mixed together.
S4, coating the solution A on a polyacrylonitrile-based membrane, drying for 2h at 60 ℃, soaking in deionized water at 80 ℃ for 12h, and vacuum drying at 40 ℃ for 10h to obtain a polyacrylonitrile battery diaphragm; the dosage of the solution A is 50 mu L of solution A coated on each square centimeter of polyacrylonitrile-based film.
The stabilizer is silicon dioxide.
Example 4
S1, dissolving a high molecular polymer in N-methyl pyrrolidone to obtain a solution A with the high molecular polymer mass fraction of 12%; the polybenzimidazole accounts for 30 wt% of the high molecular polymer, and the perfluorosulfonic acid polymer accounts for 70 wt%;
s2, adding a stabilizer, polyacrylonitrile and polyvinylpyrrolidone into N, N-dimethylacetamide, stirring at 70 ℃ for 24 hours at a rotating speed of 500r/min, and standing in the dark for 24 hours to eliminate bubbles to obtain a solution B; the mass ratio of the stabilizer to the polyacrylonitrile to the polyvinylpyrrolidone to the N, N-dimethylacetamide is 0.6: 14: 2: 84;
s3, uniformly coating the solution B on a clean glass plate, and after coating, exposing the glass plate to the conditions of 50 ℃ and 90% of humidity and standing for 10min to form a film; then, putting the film and the glass plate into a solidification liquid for soaking for 60s (ensuring that the solidification liquid can submerge the glass plate and the film); tearing off the film, washing with deionized water, and vacuum drying at 70 ℃ for 5h to obtain a polyacrylonitrile-based film; the thickness of the polyacrylonitrile-based film is controlled to be 70 mu m; the coagulating liquid is prepared from N, N-dimethylacetamide and deionized water according to a volume ratio of 3: 20 are mixed together.
S4, coating the solution A on a polyacrylonitrile-based membrane, drying for 2h at 60 ℃, soaking in deionized water at 80 ℃ for 12h, and vacuum drying at 40 ℃ for 10h to obtain a polyacrylonitrile battery diaphragm; the dosage of the solution A is 50 mu L of solution A coated on each square centimeter of polyacrylonitrile-based film.
The stabilizer is silicon dioxide.
Comparative example 1
S1, dissolving a high molecular polymer in N-methyl pyrrolidone to obtain a solution A with the high molecular polymer mass fraction of 12%; the polybenzimidazole accounts for 30 wt% of the high molecular polymer, and the perfluorosulfonic acid polymer accounts for 70 wt%;
s2 adding polyacrylonitrile and polyvinylpyrrolidone into N, N-dimethylacetamide, stirring at 70 ℃ for 24h at a rotating speed of 500r/min, and standing in the dark for 24h to eliminate bubbles to obtain a solution B; the mass ratio of polyacrylonitrile, polyvinylpyrrolidone and N, N-dimethylacetamide is 7: 1: 42;
s3, uniformly coating the solution B on a clean glass plate, and after coating, exposing the glass plate to the conditions of 50 ℃ and 90% of humidity and standing for 10min to form a film; then, putting the film and the glass plate into a solidification liquid for soaking for 60s (ensuring that the solidification liquid can submerge the glass plate and the film); tearing off the film, washing with deionized water, and vacuum drying at 70 ℃ for 5h to obtain a polyacrylonitrile-based film; the thickness of the polyacrylonitrile-based film is controlled to be 70 mu m; the coagulating liquid is prepared from N, N-dimethylacetamide and deionized water according to a volume ratio of 3: 20 are mixed together.
S4, coating the solution A on a polyacrylonitrile-based membrane, drying for 2h at 60 ℃, soaking in deionized water at 80 ℃ for 12h, and vacuum drying at 40 ℃ for 10h to obtain a polyacrylonitrile battery diaphragm; the dosage of the solution A is 50 mu L of solution A coated on each square centimeter of polyacrylonitrile-based film.
Example 5
S1, dissolving a high molecular polymer in N-methyl pyrrolidone to obtain a solution A with the high molecular polymer mass fraction of 12%; the polybenzimidazole accounts for 30 wt% of the high molecular polymer, and the perfluorosulfonic acid polymer accounts for 70 wt%;
s2, adding a stabilizer, polyacrylonitrile and polyvinylpyrrolidone into N, N-dimethylacetamide, stirring at 70 ℃ for 24 hours at a rotating speed of 500r/min, and standing in the dark for 24 hours to eliminate bubbles to obtain a solution B; the mass ratio of the stabilizer to the polyacrylonitrile to the polyvinylpyrrolidone to the N, N-dimethylacetamide is 0.6: 14: 2: 84;
s3, uniformly coating the solution B on a clean glass plate, and after coating, exposing the glass plate to the conditions of 50 ℃ and 90% of humidity and standing for 10min to form a film; then, putting the film and the glass plate into a solidification liquid for soaking for 60s (ensuring that the solidification liquid can submerge the glass plate and the film); tearing off the film, washing with deionized water, and vacuum drying at 70 ℃ for 5h to obtain a polyacrylonitrile-based film; the thickness of the polyacrylonitrile-based film is controlled to be 70 mu m; the coagulating liquid is prepared from N, N-dimethylacetamide and deionized water according to a volume ratio of 3: 20 are mixed together.
S4, coating the solution A on a polyacrylonitrile-based membrane, drying for 2h at 60 ℃, soaking in deionized water at 80 ℃ for 12h, and vacuum drying at 40 ℃ for 10h to obtain a polyacrylonitrile battery diaphragm; the dosage of the solution A is 50 mu L of solution A coated on each square centimeter of polyacrylonitrile-based film.
The stabilizing agent is montmorillonite.
Example 6
S1, dissolving a high molecular polymer in N-methyl pyrrolidone to obtain a solution A with the high molecular polymer mass fraction of 12%; the polybenzimidazole accounts for 30 wt% of the high molecular polymer, and the perfluorosulfonic acid polymer accounts for 70 wt%;
s2, adding a stabilizer, polyacrylonitrile and polyvinylpyrrolidone into N, N-dimethylacetamide, stirring at 70 ℃ for 24 hours at a rotating speed of 500r/min, and standing in the dark for 24 hours to eliminate bubbles to obtain a solution B; the mass ratio of the stabilizer to the polyacrylonitrile to the polyvinylpyrrolidone to the N, N-dimethylacetamide is 0.6: 14: 2: 84;
s3, uniformly coating the solution B on a clean glass plate, and after coating, exposing the glass plate to the conditions of 50 ℃ and 90% of humidity and standing for 10min to form a film; then, putting the membrane and the glass plate into a solidification liquid for soaking for 60s (ensuring that the solidification liquid can submerge the glass plate and the membrane); tearing off the film, washing with deionized water, and vacuum drying at 70 ℃ for 5h to obtain a polyacrylonitrile-based film; the thickness of the polyacrylonitrile-based film is controlled to be 70 mu m; the coagulating liquid is prepared from N, N-dimethylacetamide and deionized water according to a volume ratio of 3: 20 are mixed together.
S4, coating the solution A on a polyacrylonitrile-based membrane, drying for 2h at 60 ℃, soaking in deionized water at 80 ℃ for 12h, and vacuum drying at 40 ℃ for 10h to obtain a polyacrylonitrile battery diaphragm; the dosage of the solution A is 50 mu L of solution A coated on each square centimeter of polyacrylonitrile-based film.
The stabilizer is organic montmorillonite.
The preparation method of the organic montmorillonite comprises the following steps: dispersing 2g of montmorillonite powder in 40mL of water, and stirring at 50 ℃ and a rotating speed of 300r/min for 60min to obtain montmorillonite dispersion liquid; adding 0.8g of hexadecyl trimethyl ammonium bromide into 10mL of water with the temperature of 90 ℃ and stirring for 10min at the rotating speed of 200r/min to obtain a hexadecyl trimethyl ammonium bromide aqueous solution; dropping hexadecyl trimethyl ammonium bromide aqueous solution with the temperature of 90 ℃ into montmorillonite dispersion liquid with the temperature of 50 ℃ at the speed of 0.05g/s under stirring at the rotating speed of 300r/min, stirring for 6 hours at the rotating speed of 300r/min under water bath with the temperature of 50 ℃ after dropping is finished, performing suction filtration by using conventional filter paper, washing the obtained solid by deionized water until the solid does not contain bromide ions (detected by silver nitrate), drying the obtained solid for 24 hours at the temperature of 80 ℃ and the vacuum degree of 0.02MPa, and grinding into powder to obtain the organic montmorillonite.
Example 7
S1, dissolving a high molecular polymer in N-methyl pyrrolidone to obtain a solution A with the high molecular polymer mass fraction of 12%; the polybenzimidazole accounts for 30 wt% of the high molecular polymer, and the perfluorosulfonic acid polymer accounts for 70 wt%;
s2, adding a stabilizer, polyacrylonitrile and polyvinylpyrrolidone into N, N-dimethylacetamide, stirring at 70 ℃ for 24 hours at a rotating speed of 500r/min, and standing in the dark for 24 hours to eliminate bubbles to obtain a solution B; the mass ratio of the stabilizer to the polyacrylonitrile to the polyvinylpyrrolidone to the N, N-dimethylacetamide is 0.6: 14: 2: 84;
s3, uniformly coating the solution B on a clean glass plate, and after coating, exposing the glass plate to the conditions of 50 ℃ and 90% of humidity and standing for 10min to form a film; then, putting the membrane and the glass plate into a solidification liquid for soaking for 60s (ensuring that the solidification liquid can submerge the glass plate and the membrane); tearing off the film, washing with deionized water, and vacuum drying at 70 ℃ for 5h to obtain a polyacrylonitrile-based film; the thickness of the polyacrylonitrile-based film is controlled to be 70 mu m; the coagulating liquid is prepared from N, N-dimethylacetamide and deionized water according to a volume ratio of 3: 20 are mixed together.
S4, coating the solution A on a polyacrylonitrile-based membrane, drying for 2h at 60 ℃, soaking in deionized water at 80 ℃ for 12h, and vacuum drying at 40 ℃ for 10h to obtain a polyacrylonitrile battery diaphragm; the dosage of the solution A is 50 mu L of solution A coated on each square centimeter of polyacrylonitrile-based film.
The stabilizer is organic montmorillonite and silicon dioxide according to the mass ratio of 5: 1.
the preparation method of the organic montmorillonite comprises the following steps: dispersing 2g of montmorillonite powder in 40mL of water, and stirring at 50 ℃ and a rotating speed of 300r/min for 60min to obtain montmorillonite dispersion liquid; adding 0.8g of hexadecyl trimethyl ammonium bromide into 10mL of water with the temperature of 90 ℃ and stirring for 10min at the rotating speed of 200r/min to obtain a hexadecyl trimethyl ammonium bromide aqueous solution; dropping hexadecyl trimethyl ammonium bromide aqueous solution with the temperature of 90 ℃ into montmorillonite dispersion liquid with the temperature of 50 ℃ at the speed of 0.05g/s under stirring at the rotating speed of 300r/min, stirring for 6 hours at the rotating speed of 300r/min under water bath with the temperature of 50 ℃ after dropping is finished, performing suction filtration by using conventional filter paper, washing the obtained solid by deionized water until the solid does not contain bromide ions (detected by silver nitrate), drying the obtained solid for 24 hours at the temperature of 80 ℃ and the vacuum degree of 0.02MPa, and grinding into powder to obtain the organic montmorillonite.
Example 8
S1, dissolving a high molecular polymer in N-methyl pyrrolidone to obtain a solution A with the high molecular polymer mass fraction of 12%; the polybenzimidazole accounts for 30 wt% of the high molecular polymer, and the perfluorosulfonic acid polymer accounts for 70 wt%;
s2, adding a stabilizer, polyacrylonitrile and polyvinylpyrrolidone into N, N-dimethylacetamide, stirring at 70 ℃ for 24 hours at a rotating speed of 500r/min, and standing in the dark for 24 hours to eliminate bubbles to obtain a solution B; the mass ratio of the stabilizer to the polyacrylonitrile to the polyvinylpyrrolidone to the N, N-dimethylacetamide is 0.6: 14: 2: 84;
s3, uniformly coating the solution B on a clean glass plate, and after coating, exposing the glass plate to the conditions of 50 ℃ and 90% of humidity and standing for 10min to form a film; then, putting the membrane and the glass plate into a solidification liquid for soaking for 60s (ensuring that the solidification liquid can submerge the glass plate and the membrane); tearing off the film, washing with deionized water, and vacuum drying at 70 ℃ for 5h to obtain a polyacrylonitrile-based film; the thickness of the polyacrylonitrile-based film is controlled to be 70 mu m; the coagulating liquid is prepared from N, N-dimethylacetamide and deionized water according to a volume ratio of 3: 20 are mixed together.
S4, coating the solution A on a polyacrylonitrile-based membrane, drying for 2h at 60 ℃, soaking in deionized water at 80 ℃ for 12h, and vacuum drying at 40 ℃ for 10h to obtain a polyacrylonitrile battery diaphragm; the dosage of the solution A is 50 mu L of solution A coated on each square centimeter of polyacrylonitrile-based film.
The stabilizing agent is montmorillonite and silicon dioxide according to the mass ratio of 5: 1.
test example 1
Testing of tensile Strength:
reference is made to GB/T1040.3-2006 section 3 for determination of tensile Properties of plastics: the polyacrylonitrile battery separators obtained in examples 2 to 8 and comparative example 1 were cut and tested for tensile strength according to the sample sizes specified in test conditions for films and sheets.
Testing the thermal shrinkage rate: the polyacrylonitrile battery diaphragm obtained in the embodiments 2-8 and the comparative example 1 is cut into a wafer with the diameter of 19mm, then the wafer is heated in an oven at 150 ℃ for 1 hour, and then the membrane is taken out to measure the diameter, and the thermal shrinkage rate is calculated. The mechanical properties of the separator are shown in table 1.
Table 1: mechanical property of diaphragm
| Examples | Longitudinal tensile Strength (MPa) | Thermal shrinkage (%) |
| Example 2 | 174 | 1.5 |
| Example 3 | 168 | 1.6 |
| Example 4 | 184 | 1.2 |
| Comparative example 1 | 123 | 3.8 |
| Example 5 | 181 | 1.4 |
| Example 6 | 204 | 0.9 |
| Example 7 | 226 | 0.4 |
| Example 8 | 208 | 0.8 |
Test example 2
Ion conductivity test referring to "preparation and performance study of separator for zinc bromine flow battery" 2015 university specialty academic master degree paper 2.4.5 single cell assembly and performance test specified method of the invention polyacrylonitrile battery separator was single cell assembled and the conductivity of the separator was tested as shown in table 2.
Table 2: conductivity meter
| Conductivity (S/cm) | |
| Example 2 | 0.0034 |
| Example 3 | 0.0064 |
| Example 4 | 0.0081 |
| Example 5 | 0.0073 |
| Example 6 | 0.0092 |
| Example 7 | 0.0153 |
| Example 8 | 0.0109 |
Some of the raw material sources in the examples are as follows:
polybenzimidazole: molecular weight about 25 million, powder, Suzhou Qi Heng plastication Limited.
Perfluorosulfonic acid polymer: nafion for short, model: n836376Nafion R-1100 resin, Jining HuaKai resin Co., Ltd.
N-methylpyrrolidone: CAS number: 872-50-4.
Polyacrylonitrile: the model is as follows: P60C, molecular weight 15 ten thousand, shaoxing jima composite limited.
Polyvinylpyrrolidone: CAS number: 9003-39-8, model number PVPk30, molecular weight: 4 ten thousand.
N, N-dimethylacetamide: CAS number: 127-19-5.
Montmorillonite and montmorillonite powder: particle size of 3000 meshes and specific surface area of 240m2(g) Gangshou county Changchang mineral processing factory.
Silicon dioxide: fumed silica, also known as white carbon black, with a particle size of 10-20 nm, Shandong Youso chemical technology, Inc.
Cetyl trimethylammonium bromide: CAS number: 57-09-0.
Examples 9 to 16
A zinc-bromine flow battery comprises a positive plate, a negative plate and a battery diaphragm arranged between the positive plate and the negative plate.
The positive plate is a graphite plate (purchased from Zibo European positive carbon Co., Ltd., length, width and thickness of 6cm, 6cm and 0.5 cm).
The negative plate is a graphite plate (purchased from Zibo Euro positive carbon Co., Ltd., length x width x thickness of 6cm x 0.5 cm).
The battery separators of examples 9-15 correspond to the polyacrylonitrile battery separators prepared in examples 2-8, respectively.
The battery separator of example 16 was a polyacrylonitrile battery separator prepared in comparative example 1.
The zinc-bromine flow battery also comprises electrolyte which is commonly used in the industry, and the electrolyte which consists of 2.5mol/L zinc bromide, 2.5mol/L sodium chloride and the balance of water is adopted in the embodiments 9 to 16.
Test example 3:
and (3) testing the charging and discharging efficiency: the zinc-bromine flow batteries of examples 9-16 were assembled according to the "preparation of separator for zinc-bromine flow batteries and performance study" 2015 university specialty Master department paper 2.4.5 assembly of single cells. And (3) performing a charge-discharge cycle test at 1C between 3.0 and 4.2V, circulating for 50 times, and calculating the charge-discharge efficiency.
The charge-discharge efficiency refers to the ratio of the capacity obtained by discharging divided by the capacity provided by the previous charging step. In other words, the charge-discharge efficiency, CEfficiency of＝Dn+1/CnX 100%, where D is the discharge capacity, C is the charge capacity, and n is the number of cycles. The charge and discharge efficiency is shown in table 3.
Table 3: charge-discharge efficiency meter
The battery diaphragm of the zinc-bromine flow battery prepared by the invention has longitudinal tensile strength of more than 168MPa and thermal shrinkage of less than 1.2 percent, and has excellent mechanical properties. The zinc-bromine flow battery can be charged and discharged for a long time with large capacity, and the charging and discharging efficiency is high. Moreover, the battery diaphragm also has higher conductivity. The higher the conductivity, the lower the resistance, which means that the barrier ability of the separator to the flow of electrons is smaller, and the electrochemical performance of the separator is more excellent.
Claims (2)
1. The utility model provides a zinc bromine redox flow battery, includes positive plate, negative pole piece and sets up battery diaphragm between positive plate and the negative pole piece which characterized in that:
the positive plate is one of a graphite plate, a carbon felt, a graphite felt or a carbon cloth;
the negative plate is one of a graphite plate, a carbon felt, a graphite felt or a carbon cloth;
the battery diaphragm is a polyacrylonitrile battery diaphragm;
the polyacrylonitrile battery diaphragm is prepared by the following method:
s1, dissolving a high molecular polymer in an organic solvent to obtain a solution A with the high molecular polymer mass fraction of 10-15%;
s2, adding a stabilizer, polyacrylonitrile and polyvinylpyrrolidone into N, N-dimethylacetamide, stirring at the rotating speed of 300-500 r/min for 20-30 h at the temperature of 60-80 ℃, and standing in a dark place for 20-30 h to obtain a solution B; the mass ratio of the stabilizer to the polyacrylonitrile to the polyvinylpyrrolidone to the N, N-dimethylacetamide is (0.5-0.8): (10-15): (1-3): (70-85);
s3, uniformly blade-coating the solution B on a clean glass plate, and after blade-coating, standing for 5-10 min under the conditions that the temperature is 35-50 ℃ and the humidity is 70-90% to form a film; then immersing the film and the glass plate into a solidification solution for 60-80 s; tearing off the film, washing with water, and vacuum-drying at 60-80 ℃ for 4-8 h to obtain a polyacrylonitrile-based film; the thickness of the polyacrylonitrile-based film is controlled to be 50-80 mu m; the solidification liquid is prepared from N, N-dimethylacetamide and water in a volume ratio of (2-5): 20 are mixed;
s4, coating the solution A on a polyacrylonitrile base film, drying for 1.5-3 h at 50-70 ℃, soaking in 75-90 ℃ water for 10-15 h, and vacuum drying for 6-10 h at 40-60 ℃ to obtain the polyacrylonitrile battery diaphragm; the dosage of the solution A is 40-60 mu L of solution A coated on each square centimeter of polyacrylonitrile-based film;
the polybenzimidazole accounts for 30 wt% of the high molecular polymer, and the perfluorosulfonic acid polymer accounts for 70 wt%;
the stabilizer is organic montmorillonite and silicon dioxide according to the mass ratio of 5: 1;
the preparation method of the organic montmorillonite comprises the following steps: dispersing 1-3 g of montmorillonite powder in 30-50 mL of water, and stirring at 45-60 ℃ and at a rotating speed of 300-500 r/min for 40-80 min to obtain montmorillonite dispersion liquid; adding 0.7-1.1 g of hexadecyl trimethyl ammonium bromide into 8-12 mL of water with the temperature of 80-90 ℃, and stirring at the rotating speed of 100-300 r/min for 5-10 min to obtain a hexadecyl trimethyl ammonium bromide aqueous solution; dropping hexadecyl trimethyl ammonium bromide aqueous solution into the montmorillonite dispersion liquid at the speed of 0.05-0.1 g/s under stirring at the rotating speed of 100-300 r/min, continuing stirring at the rotating speed of 100-300 r/min for 5-8 h after dropping, performing suction filtration, washing the obtained solid with water until no bromide ion is contained, performing vacuum drying on the obtained solid at the temperature of 70-90 ℃ for 20-30 h, and grinding into powder to obtain the organic montmorillonite.
2. The zinc-bromine flow battery of claim 1, wherein: the organic solvent in step S1 is one of dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, and N, N-dimethylacetamide.
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