CN108376788B - Zinc-bromine flow battery pole plate - Google Patents
Zinc-bromine flow battery pole plate Download PDFInfo
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- CN108376788B CN108376788B CN201810165266.XA CN201810165266A CN108376788B CN 108376788 B CN108376788 B CN 108376788B CN 201810165266 A CN201810165266 A CN 201810165266A CN 108376788 B CN108376788 B CN 108376788B
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
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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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- 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
Abstract
The invention discloses a zinc-bromine flow battery pole plate. The novel graphite electrode plate with excellent conductivity is prepared by adding a novel material, namely a zeolite imidazole ester framework structure nano carbon sheet, into traditional petroleum coke and asphalt. Meanwhile, the invention also adds the reinforcing particles for improving the deformation resistance of the graphite electrode, so that the zinc-bromine flow battery pole plate prepared by the invention has excellent conductivity and deformation resistance.
Description
Technical Field
The invention relates to a battery polar plate, in particular to a zinc-bromine flow battery polar plate.
Background
At present, the storage battery used in an independent energy system such as a distributed energy system is generally a lead-acid battery, and the lead-acid battery has fatal defects in both self performance and environment, for example, the lead-acid battery generally has short service life in a hot climate environment, and is more serious particularly in deep discharge; meanwhile, lead-acid batteries are also harmful to the environment because their main component is lead, which may cause serious environmental problems in production and disposal.
The zinc liquid flow battery is a liquid flow energy storage battery. 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 liquid 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 the zinc flow battery 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.
In the aspect of practicability, the carbon material is the most attractive electrode material of various super capacitors at present, and is almost a common choice for all capacitor products in the market; conductive polymers, metal oxides, and the like are being sought as electrode materials, and although they have already been applied to the commercial field, they are still far from being developed and utilized on a large scale. In future, research on electrode materials of super capacitors focuses on preparation processes and structural optimization of existing materials, and the method has the advantages of developing new materials of faradaic capacitors and double electric layer capacitors and producing high-performance materials on a large scale so as to meet the requirements of the market on the mobile power supply technology with high performance, low cost and stable performance.
The electrolyte of the zinc-bromine flow battery has certain corrosivity, the long-term circulating soaking of the electrolyte has certain corrosion swelling effect on the internal structure of the battery, the deformation of an internal polar plate and a diaphragm can be inevitably caused due to the effect for a long time, and the deformed polar plate and the diaphragm can form a blocking effect on the internal flow of the battery, so that the utilization rate of the battery is seriously influenced; as the battery operates, the deformation gradually deteriorates and the battery efficiency gradually decreases.
Therefore, the invention provides the zinc-bromine flow battery plate which has excellent conductivity and deformation resistance.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention develops a zinc-bromine flow battery plate, which is characterized in that: the polar plate comprises a positive plate and a negative plate.
Preferably, the positive plate is a zeolite imidazole ester framework structure nano carbon sheet graphite plate; the negative plate is one of a graphite plate, a carbon felt, a graphite felt or a carbon cloth.
Preferably, the carbon felt is a commercially available carbon felt or is prepared by the following method: short carbon fibers with the length of 2-5 mm, water-soluble phenolic resin, polyethylene glycol 200 and water are mixed according to the mass ratio of 1: (3-5): (0.3-0.8): (10-16), stirring and dispersing for 30-50 min under the condition of 200-500 revolutions per minute; pouring the mixture into a mold, pressurizing to remove water, and then curing and drying at the constant temperature of 120-200 ℃ for 1-3 h to form a carbon felt biscuit; and (3) demolding the carbon felt biscuit, then carrying out carbonization treatment at the constant temperature of 700-1000 ℃ for 1-3 h, then carrying out constant temperature of 1700-2000 ℃ for 1-2 h in a nitrogen atmosphere, and cooling to room temperature to obtain the carbon felt.
Preferably, the preparation method of the zeolite imidazolate framework structure nano carbon sheet graphite plate comprises the following steps:
s1, batching:
kneading petroleum coke and asphalt to form a core slurry; adding the zeolite imidazole ester framework structure nano carbon sheet into a dispersing agent at the temperature of 10-35 ℃, and ultrasonically dispersing for 10-30 min to prepare a zeolite imidazole ester framework structure nano carbon sheet dispersion liquid with the concentration of 20-50 mg/mL; kneading zeolite imidazole ester framework structure nano carbon sheet dispersion liquid, petroleum coke, asphalt and reinforced particles to form surface sizing agent;
s2 blank forming:
a co-extrusion machine is adopted to match with the double-layer co-extrusion die orifice, so that the surface slurry is wrapped by the core slurry; then pressurizing, drying and shaping the raw materials together to form a composite green body; the extrusion temperature in the pressure drying and shaping is controlled to be 105-125 ℃, the extrusion pressure is controlled to be 10-18 MPa, the pressure maintaining time is controlled to be 5-10 min,
s3 graphitization treatment:
the composite green compact obtained in the step S2 is subjected to conventional roasting and graphitization high-temperature treatment, and then is cut into a required shape according to production requirements, so that the zeolite imidazole ester framework structure nano carbon sheet graphite plate is obtained; the roasting temperature is controlled to be 1000-1250 ℃, the roasting time is 10-30 days, the graphitization high-temperature treatment is controlled to be 2700-3400 ℃, and the graphitization high-temperature treatment time is 15-50 hours.
Preferably, the mass ratio of the petroleum coke to the asphalt in the core slurry is (3-6) to (1-3).
Preferably, the mass ratio of the zeolite imidazole ester framework structure nano carbon sheet dispersion liquid, the petroleum coke, the asphalt and the reinforcing particles in the surface sizing agent is 1 (10-15): (3-5): 1-2.
In the prior art, CN106588016A discloses a graphene oxide electrode, which is prepared by adding graphene oxide to a conventional graphite electrode paste. Due to the fact that the graphene is high in strength and excellent in electron transfer performance, the bending strength of the graphite electrode product can be improved and the resistivity can be degraded when the graphene electrode is applied to the graphite electrode. However, the application of graphene in graphite electrodes has certain defects: firstly, the synthesis process of graphene is complex, the yield is low, and the industrial cost is high; secondly, a large amount of acid liquor is used in the preparation process of the graphene, so that the environment is easily polluted; finally, graphene sheets tend to aggregate to become graphite under strong van der waals attraction, thereby losing the properties of graphene.
The zeolite imidazole ester framework structure nano carbon sheet added in the invention belongs to metal organic framework Materials (MOFs) with ordered structures. The zeolite imidazole ester framework structure nano carbon sheet has a high specific surface area and a rich pore structure.
Preferably, the reinforcing particles are one or a mixture of more of tungsten oxide carbon nanotubes, boron carbide micro powder and silicon carbide micro powder.
Preferably, the mass ratio of the core part sizing agent to the surface sizing agent is 10 (2-5).
Preferably, the preparation method of the zeolite imidazolate framework structure nano carbon sheet comprises the following steps:
a, dissolving 0.9-1.1 g of zinc acetate in 250-300 mL of water to obtain a zinc acetate aqueous solution; dissolving 2.8-3.2 g of 2-methylimidazole in 250-300 mL of water to obtain a 2-methylimidazole water solution; dropwise adding a 2-methylimidazole water solution into a zinc acetate water solution at the speed of 0.02-0.05 g/s at the temperature of 10-35 ℃ at 200-500 r/min, continuously stirring for 20-36 hours at the temperature of 10-35 ℃ at 200-500 r/min after dropwise adding, filtering, washing, and drying for 24-48 hours at the temperature of 40-60 ℃ to obtain a zeolite imidazole ester framework material;
and B, heating the zeolite imidazole ester framework structure material from 10-35 ℃ to 800-1000 ℃ at a heating rate of 3-5 ℃/min in a nitrogen atmosphere, preserving heat at 800-1000 ℃ for 1-3 h, then heating from 800-1000 ℃ to 1200-1400 ℃ at a heating rate of 5-10 ℃/min in a carbon dioxide atmosphere, preserving heat at 1200-1400 ℃ for 1.5-3 h, and naturally cooling to room temperature to obtain the zeolite imidazole ester framework structure nano carbon sheet.
Preferably, the dispersant is one or more of absolute ethyl alcohol, N-dimethylformamide and tetrahydrofuran.
Preferably, the power of the ultrasonic dispersion in the step S1 is 150-300W, and the frequency is 24-40 KHz.
The invention has the beneficial effects that:
the zinc-bromine flow battery pole plate prepared by the invention has good conductivity, the resistivity of the zinc-bromine flow battery pole plate is less than 6.3 mu omega cm, and meanwhile, the zinc-bromine flow battery pole plate also has excellent deformation resistance. The polar plate can keep the initial appearance for a long time in the long-term circulating soaking of the electrolyte, thereby prolonging the service life of the battery.
Detailed Description
Example 1
A zinc-bromine flow battery polar plate comprises a positive plate and a negative plate.
The positive plate is a graphite plate made of zeolite imidazole ester framework material.
The negative plate is a graphite plate (purchased from Zibo Europe positive carbon Co., Ltd., length x width x thickness of 6cm x 0.5 cm).
The preparation method of the zeolite imidazole ester framework material graphite plate comprises the following steps:
s1, batching:
mixing petroleum coke and asphalt according to the mass ratio of 3:1, and kneading the mixture for 30min at the speed of 200r/min in an ZNH-5L kneader (New Hongda chemical machinery Co., Ltd. of Lyzhou) to form core slurry; adding the zeolite imidazole ester framework material into a dispersing agent at 25 ℃, and ultrasonically dispersing for 30min to prepare a zeolite imidazole ester framework material dispersion liquid with the concentration of 40 mg/mL; dispersing zeolite imidazole ester framework material dispersion liquid, petroleum coke and asphalt according to a mass ratio of 1: 10: 3, uniformly mixing, and kneading for 30min at 200r/min in an ZNH-5L kneader (Laizhou New Hongda chemical machinery Co., Ltd.) to form a surface sizing agent; the dispersant is N, N-dimethylformamide; the power of the ultrasonic dispersion is 300W, and the frequency is 40 KHz;
s2 blank forming:
a co-extrusion machine is adopted to match with the double-layer co-extrusion die orifice, so that the surface slurry is wrapped by the core slurry; then pressurizing, drying and shaping the raw materials together to form a composite green body; in the pressure drying and shaping, the extrusion temperature is controlled at 110 ℃, the extrusion pressure is controlled at 15MPa, and the pressure maintaining time is controlled for 10 min;
s3 graphitization treatment:
the composite green compact obtained in the step S2 is subjected to conventional roasting and graphitization high-temperature treatment, and then is cut to 6cm multiplied by 0.5cm (length multiplied by width multiplied by thickness), so that the zeolite imidazole ester framework material graphite plate is obtained; the roasting temperature is controlled to be 1200 ℃, the roasting time is 22 days, the graphitization high-temperature treatment is controlled to be 2700 ℃, and the graphitization high-temperature treatment time is 18 hours.
Finally, obtaining a positive plate of the graphite plate with the material of zeolite imidazole ester framework structure, wherein the section of the positive plate is in a shape like a Chinese character 'hui'; the outer layer is surface slurry, and the inner part is core slurry. The mass ratio of the core part slurry to the surface slurry is 10: 3.
the preparation method of the zeolite imidazole ester framework material comprises the following steps:
dissolving 0.95g of zinc acetate in 260mL of water to obtain a zinc acetate aqueous solution; 2.9g of 2-methylimidazole was dissolved in 260mL of water to obtain an aqueous solution of 2-methylimidazole; dropwise adding a 2-methylimidazole aqueous solution into a zinc acetate aqueous solution at the speed of 0.05g/s at the temperature of 25 ℃ and at the speed of 300r/min, continuously stirring for 24 hours at the temperature of 25 ℃ and at the speed of 300r/min after dropwise adding, filtering by using a 500-mesh gauze, respectively washing the obtained solid by using absolute ethyl alcohol and deionized water for 3 times, wherein the volume of the absolute ethyl alcohol or the deionized water for washing each time is 50mL, and drying for 48 hours at the temperature of 40 ℃ to obtain the zeolite imidazolate framework material.
Assembling an electrolytic cell: the positive and negative polar plates are the positive and negative polar plates of the embodiment; the diaphragm is a diaphragm of a American celgard 2400 type battery; the positive and negative electrolyte is a mixed solution consisting of 2.5mol/L zinc bromide, 2.5mol/L sodium chloride and the balance of water. The specific assembly steps refer to the preparation of the diaphragm for the zinc-bromine flow battery and the performance research of the Sun Yu 'the preparation and performance research of the diaphragm for the zinc-bromine flow battery' the assembly of the single cell in the 2.4.5 academic paper of the professional university of the major graduates of 2015 university. And carrying out a charge-discharge cycle test at room temperature at 1C between 3.0V and 4.2V. And (3) testing results: after 500 cycles, the battery capacity was 87%.
Example 2
A zinc-bromine flow battery polar plate comprises a positive plate and a negative plate.
The positive plate is a zeolite imidazole ester framework structure nano carbon sheet graphite plate.
The negative plate is a graphite plate (purchased from Zibo Europe positive carbon Co., Ltd., length x width x thickness of 6cm x 0.5 cm).
The preparation method of the zeolite imidazole ester framework structure nano carbon sheet graphite plate comprises the following steps:
s1, batching:
mixing petroleum coke and asphalt according to the mass ratio of 3:1, and kneading the mixture for 30min at the speed of 200r/min in an ZNH-5L kneader (New Hongda chemical machinery Co., Ltd. of Lyzhou) to form core slurry; adding the zeolite imidazole ester framework structure nano carbon sheet into a dispersing agent at 25 ℃, and ultrasonically dispersing for 30min to prepare a zeolite imidazole ester framework structure nano carbon sheet dispersion liquid with the concentration of 40 mg/mL; dispersing zeolite imidazole ester framework structure nano carbon sheets, petroleum coke and asphalt according to a mass ratio of 1: 10: 3, uniformly mixing, and kneading for 30min at 200r/min in an ZNH-5L kneader (Laizhou New Hongda chemical machinery Co., Ltd.) to form a surface sizing agent; the dispersant is N, N-dimethylformamide; the power of the ultrasonic dispersion is 300W, and the frequency is 40 KHz;
s2 blank forming:
a co-extrusion machine is adopted to match with the double-layer co-extrusion die orifice, so that the surface slurry is wrapped by the core slurry; then pressurizing, drying and shaping the raw materials together to form a composite green body; in the pressure drying and shaping, the extrusion temperature is controlled at 110 ℃, the extrusion pressure is controlled at 15MPa, and the pressure maintaining time is controlled for 10 min;
s3 graphitization treatment:
the composite green compact obtained in the step S2 is subjected to conventional roasting and graphitization high-temperature treatment, and then is cut to 6cm multiplied by 0.5cm (length multiplied by width multiplied by thickness), so that the zeolite imidazole ester framework structure nano carbon sheet graphite plate is obtained; the roasting temperature is controlled to be 1200 ℃, the roasting time is 22 days, the graphitization high-temperature treatment is controlled to be 2700 ℃, and the graphitization high-temperature treatment time is 18 hours.
Finally, obtaining a positive plate of the nano carbon sheet graphite plate with the material of zeolite imidazole ester framework structure, wherein the cross section of the positive plate is in a shape like Chinese character 'hui'; the outer layer is surface slurry, and the inner part is core slurry. The mass ratio of the core part slurry to the surface slurry is 10: 3.
the preparation method of the zeolite imidazole ester framework structure nano carbon sheet comprises the following steps:
a, dissolving 0.95g of zinc acetate in 260mL of water to obtain a zinc acetate aqueous solution; 2.9g of 2-methylimidazole is dissolved in 260mL of water to obtain a 2-methylimidazole aqueous solution; dropwise adding a 2-methylimidazole aqueous solution into a zinc acetate aqueous solution at the speed of 0.05g/s at the temperature of 25 ℃ and at the speed of 300r/min, continuously stirring for 24 hours at the temperature of 25 ℃ and at the speed of 300r/min after dropwise adding, filtering by using a 500-mesh gauze, respectively washing the obtained solid by using absolute ethyl alcohol and deionized water for 3 times, wherein the volume of the absolute ethyl alcohol or the deionized water after washing for each time is 50mL, and drying for 48 hours at the temperature of 40 ℃ to obtain the zeolite imidazolate framework structure material;
and B, heating the zeolite imidazole ester framework structure material from 25 ℃ to 900 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat at 900 ℃ for 2h, then heating from 900 ℃ to 1200 ℃ at a heating rate of 10 ℃/min in a carbon dioxide atmosphere, preserving heat at 1200 ℃ for 2h, and naturally cooling to room temperature to obtain the zeolite imidazole ester framework structure nano-carbon sheet.
Assembling an electrolytic cell: the positive and negative polar plates are the positive and negative polar plates of the embodiment; the diaphragm is a diaphragm of a American celgard 2400 type battery; the positive and negative electrolyte is a mixed solution consisting of 2.5mol/L zinc bromide, 2.5mol/L sodium chloride and the balance of water. The specific assembly steps refer to the preparation of the diaphragm for the zinc-bromine flow battery and the performance research of the Sun Yu 'the preparation and performance research of the diaphragm for the zinc-bromine flow battery' the assembly of the single cell in the 2.4.5 academic paper of the professional university of the major graduates of 2015 university. And carrying out a charge-discharge cycle test at room temperature at 1C between 3.0V and 4.2V. And (3) testing results: after 500 cycles, the battery capacity was 89%.
Example 3
A zinc-bromine flow battery polar plate comprises a positive plate and a negative plate.
The positive plate is a zeolite imidazole ester framework structure nano carbon sheet graphite plate.
The negative plate is a graphite plate (purchased from Zibo Europe positive carbon Co., Ltd., length x width x thickness of 6cm x 0.5 cm).
The preparation method of the zeolite imidazole ester framework structure nano carbon sheet graphite plate comprises the following steps:
s1, batching:
mixing petroleum coke and asphalt according to the mass ratio of 3:1, and kneading the mixture for 30min at the speed of 200r/min in an ZNH-5L kneader (New Hongda chemical machinery Co., Ltd. of Lyzhou) to form core slurry; adding the zeolite imidazole ester framework structure nano carbon sheet into a dispersing agent at 25 ℃, and ultrasonically dispersing for 30min to prepare a zeolite imidazole ester framework structure nano carbon sheet dispersion liquid with the concentration of 40 mg/mL; dispersing zeolite imidazole ester framework structure nano carbon sheet dispersion liquid, petroleum coke, asphalt, tungsten oxide carbon nano tubes and boron carbide micro powder in a mass ratio of 1: 10: 3: 0.75: 0.75 percent of the mixture is evenly mixed and kneaded for 30min at 200r/min in an ZNH-5L kneader (Laizhou Xin Hongda chemical machinery Co., Ltd.) to form a surface sizing agent; the dispersant is N, N-dimethylformamide; the power of the ultrasonic dispersion is 300W, and the frequency is 40 KHz;
s2 blank forming:
a co-extrusion machine is adopted to match with the double-layer co-extrusion die orifice, so that the surface slurry is wrapped by the core slurry; then pressurizing, drying and shaping the raw materials together to form a composite green body; in the pressure drying and shaping, the extrusion temperature is controlled at 110 ℃, the extrusion pressure is controlled at 15MPa, and the pressure maintaining time is controlled for 10 min;
s3 graphitization treatment:
the composite green compact obtained in the step S2 is subjected to conventional roasting and graphitization high-temperature treatment, and then is cut to 6cm multiplied by 0.5cm (length multiplied by width multiplied by thickness), so that the zeolite imidazole ester framework structure nano carbon sheet graphite plate is obtained; the roasting temperature is controlled to be 1200 ℃, the roasting time is 22 days, the graphitization high-temperature treatment is controlled to be 2700 ℃, and the graphitization high-temperature treatment time is 18 hours.
Finally, obtaining a positive plate of the nano carbon sheet graphite plate with the material of zeolite imidazole ester framework structure, wherein the cross section of the positive plate is in a shape like Chinese character 'hui'; the outer layer is surface slurry, and the inner part is core slurry. The mass ratio of the core part slurry to the surface slurry is 10: 3.
the preparation method of the zeolite imidazole ester framework structure nano carbon sheet comprises the following steps:
a, dissolving 0.95g of zinc acetate in 260mL of water to obtain a zinc acetate aqueous solution; 2.9g of 2-methylimidazole is dissolved in 260mL of water to obtain a 2-methylimidazole aqueous solution; dropwise adding a 2-methylimidazole aqueous solution into a zinc acetate aqueous solution at the speed of 0.05g/s at the temperature of 25 ℃ and at the speed of 300r/min, continuously stirring for 24 hours at the temperature of 25 ℃ and at the speed of 300r/min after dropwise adding, filtering by using a 500-mesh gauze, respectively washing the obtained solid by using absolute ethyl alcohol and deionized water for 3 times, wherein the volume of the absolute ethyl alcohol or the deionized water after washing for each time is 50mL, and drying for 48 hours at the temperature of 40 ℃ to obtain the zeolite imidazolate framework structure material;
and B, heating the zeolite imidazole ester framework structure material from 25 ℃ to 900 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat at 900 ℃ for 2h, then heating from 900 ℃ to 1200 ℃ at a heating rate of 10 ℃/min in a carbon dioxide atmosphere, preserving heat at 1200 ℃ for 2h, and naturally cooling to room temperature to obtain the zeolite imidazole ester framework structure nano-carbon sheet.
Assembling an electrolytic cell: the positive and negative polar plates are the positive and negative polar plates of the embodiment; the diaphragm is a diaphragm of a American celgard 2400 type battery; the positive and negative electrolyte is a mixed solution consisting of 2.5mol/L zinc bromide, 2.5mol/L sodium chloride and the balance of water. The specific assembly steps refer to the preparation of the diaphragm for the zinc-bromine flow battery and the performance research of the Sun Yu 'the preparation and performance research of the diaphragm for the zinc-bromine flow battery' the assembly of the single cell in the 2.4.5 academic paper of the professional university of the major graduates of 2015 university. And carrying out a charge-discharge cycle test at room temperature at 1C between 3.0V and 4.2V. And (3) testing results: after 500 cycles, the battery capacity was 92%.
Example 4
A zinc-bromine flow battery polar plate comprises a positive plate and a negative plate.
The positive plate is a zeolite imidazole ester framework structure nano carbon sheet graphite plate.
The negative plate is a graphite plate (purchased from Zibo Europe positive carbon Co., Ltd., length x width x thickness of 6cm x 0.5 cm).
The preparation method of the zeolite imidazole ester framework structure nano carbon sheet graphite plate comprises the following steps:
s1, batching:
mixing petroleum coke and asphalt according to the mass ratio of 3:1, and kneading the mixture for 30min at the speed of 200r/min in an ZNH-5L kneader (New Hongda chemical machinery Co., Ltd. of Lyzhou) to form core slurry; adding the zeolite imidazole ester framework structure nano carbon sheet into a dispersing agent at 25 ℃, and ultrasonically dispersing for 30min to prepare a zeolite imidazole ester framework structure nano carbon sheet dispersion liquid with the concentration of 40 mg/mL; dispersing zeolite imidazole ester framework structure nano carbon sheet dispersion liquid, petroleum coke, asphalt, tungsten oxide carbon nano tubes and silicon carbide micro powder according to the mass ratio of 1: 10: 3: 0.75: 0.75 percent of the mixture is evenly mixed and kneaded for 30min at 200r/min in an ZNH-5L kneader (Laizhou Xin Hongda chemical machinery Co., Ltd.) to form a surface sizing agent; the dispersant is N, N-dimethylformamide; the power of the ultrasonic dispersion is 300W, and the frequency is 40 KHz;
s2 blank forming:
a co-extrusion machine is adopted to match with the double-layer co-extrusion die orifice, so that the surface slurry is wrapped by the core slurry; then pressurizing, drying and shaping the raw materials together to form a composite green body; in the pressure drying and shaping, the extrusion temperature is controlled at 110 ℃, the extrusion pressure is controlled at 15MPa, and the pressure maintaining time is controlled for 10 min;
s3 graphitization treatment:
the composite green compact obtained in the step S2 is subjected to conventional roasting and graphitization high-temperature treatment, and then is cut to 6cm multiplied by 0.5cm (length multiplied by width multiplied by thickness), so that the zeolite imidazole ester framework structure nano carbon sheet graphite plate is obtained; the roasting temperature is controlled to be 1200 ℃, the roasting time is 22 days, the graphitization high-temperature treatment is controlled to be 2700 ℃, and the graphitization high-temperature treatment time is 18 hours.
Finally, obtaining a positive plate of the nano carbon sheet graphite plate with the material of zeolite imidazole ester framework structure, wherein the cross section of the positive plate is in a shape like Chinese character 'hui'; the outer layer is surface slurry, and the inner part is core slurry. The mass ratio of the core part slurry to the surface slurry is 10: 3.
the preparation method of the zeolite imidazole ester framework structure nano carbon sheet comprises the following steps:
a, dissolving 0.95g of zinc acetate in 260mL of water to obtain a zinc acetate aqueous solution; 2.9g of 2-methylimidazole is dissolved in 260mL of water to obtain a 2-methylimidazole aqueous solution; dropwise adding a 2-methylimidazole aqueous solution into a zinc acetate aqueous solution at the speed of 0.05g/s at the temperature of 25 ℃ and at the speed of 300r/min, continuously stirring for 24 hours at the temperature of 25 ℃ and at the speed of 300r/min after dropwise adding, filtering by using a 500-mesh gauze, respectively washing the obtained solid by using absolute ethyl alcohol and deionized water for 3 times, wherein the volume of the absolute ethyl alcohol or the deionized water after washing for each time is 50mL, and drying for 48 hours at the temperature of 40 ℃ to obtain the zeolite imidazolate framework structure material;
and B, heating the zeolite imidazole ester framework structure material from 25 ℃ to 900 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat at 900 ℃ for 2h, then heating from 900 ℃ to 1200 ℃ at a heating rate of 10 ℃/min in a carbon dioxide atmosphere, preserving heat at 1200 ℃ for 2h, and naturally cooling to room temperature to obtain the zeolite imidazole ester framework structure nano-carbon sheet.
Assembling an electrolytic cell: the positive and negative polar plates are the positive and negative polar plates of the embodiment; the diaphragm is a diaphragm of a American celgard 2400 type battery; the positive and negative electrolyte is a mixed solution consisting of 2.5mol/L zinc bromide, 2.5mol/L sodium chloride and the balance of water. The specific assembly steps refer to the preparation of the diaphragm for the zinc-bromine flow battery and the performance research of the Sun Yu 'the preparation and performance research of the diaphragm for the zinc-bromine flow battery' the assembly of the single cell in the 2.4.5 academic paper of the professional university of the major graduates of 2015 university. And carrying out a charge-discharge cycle test at room temperature at 1C between 3.0V and 4.2V. And (3) testing results: after 500 cycles, the battery capacity was 90%.
Example 5
A zinc-bromine flow battery polar plate comprises a positive plate and a negative plate.
The positive plate is a zeolite imidazole ester framework structure nano carbon sheet graphite plate.
The negative plate is a graphite plate (purchased from Zibo Europe positive carbon Co., Ltd., length x width x thickness of 6cm x 0.5 cm).
The preparation method of the zeolite imidazole ester framework structure nano carbon sheet graphite plate comprises the following steps:
s1, batching:
mixing petroleum coke and asphalt according to the mass ratio of 3:1, and kneading the mixture for 30min at the speed of 200r/min in an ZNH-5L kneader (New Hongda chemical machinery Co., Ltd. of Lyzhou) to form core slurry; adding the zeolite imidazole ester framework structure nano carbon sheet into a dispersing agent at 25 ℃, and ultrasonically dispersing for 30min to prepare a zeolite imidazole ester framework structure nano carbon sheet dispersion liquid with the concentration of 40 mg/mL; dispersing zeolite imidazole ester framework structure nano carbon sheet dispersion liquid, petroleum coke, asphalt, boron carbide micro powder and silicon carbide micro powder in a mass ratio of 1: 10: 3: 0.75: 0.75 percent of the mixture is evenly mixed and kneaded for 30min at 200r/min in an ZNH-5L kneader (Laizhou Xin Hongda chemical machinery Co., Ltd.) to form a surface sizing agent; the dispersant is N, N-dimethylformamide; the power of the ultrasonic dispersion is 300W, and the frequency is 40 KHz;
s2 blank forming:
a co-extrusion machine is adopted to match with the double-layer co-extrusion die orifice, so that the surface slurry is wrapped by the core slurry; then pressurizing, drying and shaping the raw materials together to form a composite green body; in the pressure drying and shaping, the extrusion temperature is controlled at 110 ℃, the extrusion pressure is controlled at 15MPa, and the pressure maintaining time is controlled for 10 min;
s3 graphitization treatment:
the composite green compact obtained in the step S2 is subjected to conventional roasting and graphitization high-temperature treatment, and then is cut to 6cm multiplied by 0.5cm (length multiplied by width multiplied by thickness), so that the zeolite imidazole ester framework structure nano carbon sheet graphite plate is obtained; the roasting temperature is controlled to be 1200 ℃, the roasting time is 22 days, the graphitization high-temperature treatment is controlled to be 2700 ℃, and the graphitization high-temperature treatment time is 18 hours.
Finally, obtaining a positive plate of the nano carbon sheet graphite plate with the material of zeolite imidazole ester framework structure, wherein the cross section of the positive plate is in a shape like Chinese character 'hui'; the outer layer is surface slurry, and the inner part is core slurry. The mass ratio of the core part slurry to the surface slurry is 10: 3.
the preparation method of the zeolite imidazole ester framework structure nano carbon sheet comprises the following steps:
a, dissolving 0.95g of zinc acetate in 260mL of water to obtain a zinc acetate aqueous solution; 2.9g of 2-methylimidazole is dissolved in 260mL of water to obtain a 2-methylimidazole aqueous solution; dropwise adding a 2-methylimidazole aqueous solution into a zinc acetate aqueous solution at the speed of 0.05g/s at the temperature of 25 ℃ and at the speed of 300r/min, continuously stirring for 24 hours at the temperature of 25 ℃ and at the speed of 300r/min after dropwise adding, filtering by using a 500-mesh gauze, respectively washing the obtained solid by using absolute ethyl alcohol and deionized water for 3 times, wherein the volume of the absolute ethyl alcohol or the deionized water after washing for each time is 50mL, and drying for 48 hours at the temperature of 40 ℃ to obtain the zeolite imidazolate framework structure material;
and B, heating the zeolite imidazole ester framework structure material from 25 ℃ to 900 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat at 900 ℃ for 2h, then heating from 900 ℃ to 1200 ℃ at a heating rate of 10 ℃/min in a carbon dioxide atmosphere, preserving heat at 1200 ℃ for 2h, and naturally cooling to room temperature to obtain the zeolite imidazole ester framework structure nano-carbon sheet.
Assembling an electrolytic cell: the positive and negative polar plates are the positive and negative polar plates of the embodiment; the diaphragm is a diaphragm of a American celgard 2400 type battery; the positive and negative electrolyte is a mixed solution consisting of 2.5mol/L zinc bromide, 2.5mol/L sodium chloride and the balance of water. The specific assembly steps refer to the preparation of the diaphragm for the zinc-bromine flow battery and the performance research of the Sun Yu 'the preparation and performance research of the diaphragm for the zinc-bromine flow battery' the assembly of the single cell in the 2.4.5 academic paper of the professional university of the major graduates of 2015 university. And carrying out a charge-discharge cycle test at room temperature at 1C between 3.0V and 4.2V. And (3) testing results: after 500 cycles, the battery capacity was 89%.
Example 6
A zinc-bromine flow battery polar plate comprises a positive plate and a negative plate.
The positive plate is a zeolite imidazole ester framework structure nano carbon sheet graphite plate.
The negative plate is a graphite plate (purchased from Zibo Europe positive carbon Co., Ltd., length x width x thickness of 6cm x 0.5 cm).
The preparation method of the zeolite imidazole ester framework structure nano carbon sheet graphite plate comprises the following steps:
s1, batching:
mixing petroleum coke and asphalt according to the mass ratio of 3:1, and kneading the mixture for 30min at the speed of 200r/min in an ZNH-5L kneader (New Hongda chemical machinery Co., Ltd. of Lyzhou) to form core slurry; adding the zeolite imidazole ester framework structure nano carbon sheet into a dispersing agent at 25 ℃, and ultrasonically dispersing for 30min to prepare a zeolite imidazole ester framework structure nano carbon sheet dispersion liquid with the concentration of 40 mg/mL; dispersing zeolite imidazole ester framework structure nano carbon sheet dispersion liquid, petroleum coke, asphalt, tungsten oxide carbon nano tubes, boron carbide micro powder and silicon carbide micro powder according to a mass ratio of 1: 10: 3: 0.5: 0.5: 0.5, mixing uniformly, kneading for 30min at 200r/min in an ZNH-5L kneader (Laizhou Xin Hongda chemical machinery Co., Ltd.) to form a surface sizing agent; the dispersant is N, N-dimethylformamide; the power of the ultrasonic dispersion is 300W, and the frequency is 40 KHz;
s2 blank forming:
a co-extrusion machine is adopted to match with the double-layer co-extrusion die orifice, so that the surface slurry is wrapped by the core slurry; then pressurizing, drying and shaping the raw materials together to form a composite green body; in the pressure drying and shaping, the extrusion temperature is controlled at 110 ℃, the extrusion pressure is controlled at 15MPa, and the pressure maintaining time is controlled for 10 min;
s3 graphitization treatment:
the composite green compact obtained in the step S2 is subjected to conventional roasting and graphitization high-temperature treatment, and then is cut to 6cm multiplied by 0.5cm (length multiplied by width multiplied by thickness), so that the zeolite imidazole ester framework structure nano carbon sheet graphite plate is obtained; the roasting temperature is controlled to be 1200 ℃, the roasting time is 22 days, the graphitization high-temperature treatment is controlled to be 2700 ℃, and the graphitization high-temperature treatment time is 18 hours.
Finally, obtaining a positive plate of the nano carbon sheet graphite plate with the material of zeolite imidazole ester framework structure, wherein the cross section of the positive plate is in a shape like Chinese character 'hui'; the outer layer is surface slurry, and the inner part is core slurry. The mass ratio of the core part slurry to the surface slurry is 10: 3.
the preparation method of the zeolite imidazole ester framework structure nano carbon sheet comprises the following steps:
a, dissolving 0.95g of zinc acetate in 260mL of water to obtain a zinc acetate aqueous solution; 2.9g of 2-methylimidazole is dissolved in 260mL of water to obtain a 2-methylimidazole aqueous solution; dropwise adding a 2-methylimidazole aqueous solution into a zinc acetate aqueous solution at the speed of 0.05g/s at the temperature of 25 ℃ and at the speed of 300r/min, continuously stirring for 24 hours at the temperature of 25 ℃ and at the speed of 300r/min after dropwise adding, filtering by using a 500-mesh gauze, respectively washing the obtained solid by using absolute ethyl alcohol and deionized water for 3 times, wherein the volume of the absolute ethyl alcohol or the deionized water after washing for each time is 50mL, and drying for 48 hours at the temperature of 40 ℃ to obtain the zeolite imidazolate framework structure material;
and B, heating the zeolite imidazole ester framework structure material from 25 ℃ to 900 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat at 900 ℃ for 2h, then heating from 900 ℃ to 1200 ℃ at a heating rate of 10 ℃/min in a carbon dioxide atmosphere, preserving heat at 1200 ℃ for 2h, and naturally cooling to room temperature to obtain the zeolite imidazole ester framework structure nano-carbon sheet.
Assembling an electrolytic cell: the positive and negative polar plates are the positive and negative polar plates of the embodiment; the diaphragm is a diaphragm of a American celgard 2400 type battery; the positive and negative electrolyte is a mixed solution consisting of 2.5mol/L zinc bromide, 2.5mol/L sodium chloride and the balance of water. The specific assembly steps refer to the preparation of the diaphragm for the zinc-bromine flow battery and the performance research of the Sun Yu 'the preparation and performance research of the diaphragm for the zinc-bromine flow battery' the assembly of the single cell in the 2.4.5 academic paper of the professional university of the major graduates of 2015 university. And carrying out a charge-discharge cycle test at room temperature at 1C between 3.0V and 4.2V. And (3) testing results: after 500 cycles, the battery capacity was 95%.
Example 7
A zinc-bromine flow battery polar plate comprises a positive plate and a negative plate.
The positive plate is a zeolite imidazole ester framework structure nano carbon sheet graphite plate.
The negative plate is made of carbon felt (length is 6cm multiplied by 6cm, and the specific gravity is 20 g/m)2). The preparation method comprises the following steps: short carbon fiber with the length of 4mm, water-soluble phenolic resin, polyethylene glycol 200 and water are mixed according to the mass ratio of 1: 4: 0.5: 14, mixing, stirring and dispersing for 40min under the condition of 300 revolutions per minute; pouring into a mold, pressurizing to remove water, and then curing and drying at the constant temperature of 160 ℃ for 2 hours to form a carbon felt biscuit; and (3) demolding the carbon felt biscuit, then carrying out carbonization treatment at the constant temperature of 800 ℃ for 2h, then keeping the temperature at 1800 ℃ for 2h in the nitrogen atmosphere, cooling to room temperature to obtain the carbon felt, and cutting.
The preparation method of the zeolite imidazole ester framework structure nano carbon sheet graphite plate comprises the following steps:
s1, batching:
mixing petroleum coke and asphalt according to the mass ratio of 3:1, and kneading the mixture for 30min at the speed of 200r/min in an ZNH-5L kneader (New Hongda chemical machinery Co., Ltd. of Lyzhou) to form core slurry; adding the zeolite imidazole ester framework structure nano carbon sheet into a dispersing agent at 25 ℃, and ultrasonically dispersing for 30min to prepare a zeolite imidazole ester framework structure nano carbon sheet dispersion liquid with the concentration of 40 mg/mL; dispersing zeolite imidazole ester framework structure nano carbon sheet dispersion liquid, petroleum coke, asphalt, tungsten oxide carbon nano tubes, boron carbide micro powder and silicon carbide micro powder according to a mass ratio of 1: 10: 3: 0.5: 0.5: 0.5, mixing uniformly, kneading for 30min at 200r/min in an ZNH-5L kneader (Laizhou Xin Hongda chemical machinery Co., Ltd.) to form a surface sizing agent; the dispersant is N, N-dimethylformamide; the power of the ultrasonic dispersion is 300W, and the frequency is 40 KHz;
s2 blank forming:
a co-extrusion machine is adopted to match with the double-layer co-extrusion die orifice, so that the surface slurry is wrapped by the core slurry; then pressurizing, drying and shaping the raw materials together to form a composite green body; in the pressure drying and shaping, the extrusion temperature is controlled at 110 ℃, the extrusion pressure is controlled at 15MPa, and the pressure maintaining time is controlled for 10 min;
s3 graphitization treatment:
the composite green compact obtained in the step S2 is subjected to conventional roasting and graphitization high-temperature treatment, and then is cut to 6cm multiplied by 0.5cm (length multiplied by width multiplied by thickness), so that the zeolite imidazole ester framework structure nano carbon sheet graphite plate is obtained; the roasting temperature is controlled to be 1200 ℃, the roasting time is 22 days, the graphitization high-temperature treatment is controlled to be 2700 ℃, and the graphitization high-temperature treatment time is 18 hours.
Finally, obtaining a positive plate of the nano carbon sheet graphite plate with the material of zeolite imidazole ester framework structure, wherein the cross section of the positive plate is in a shape like Chinese character 'hui'; the outer layer is surface slurry, and the inner part is core slurry. The mass ratio of the core part slurry to the surface slurry is 10: 3.
the preparation method of the zeolite imidazole ester framework structure nano carbon sheet comprises the following steps:
a, dissolving 0.95g of zinc acetate in 260mL of water to obtain a zinc acetate aqueous solution; 2.9g of 2-methylimidazole is dissolved in 260mL of water to obtain a 2-methylimidazole aqueous solution; dropwise adding a 2-methylimidazole aqueous solution into a zinc acetate aqueous solution at the speed of 0.05g/s at the temperature of 25 ℃ and at the speed of 300r/min, continuously stirring for 24 hours at the temperature of 25 ℃ and at the speed of 300r/min after dropwise adding, filtering by using a 500-mesh gauze, respectively washing the obtained solid by using absolute ethyl alcohol and deionized water for 3 times, wherein the volume of the absolute ethyl alcohol or the deionized water after washing for each time is 50mL, and drying for 48 hours at the temperature of 40 ℃ to obtain the zeolite imidazolate framework structure material;
and B, heating the zeolite imidazole ester framework structure material from 25 ℃ to 900 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat at 900 ℃ for 2h, then heating from 900 ℃ to 1200 ℃ at a heating rate of 10 ℃/min in a carbon dioxide atmosphere, preserving heat at 1200 ℃ for 2h, and naturally cooling to room temperature to obtain the zeolite imidazole ester framework structure nano-carbon sheet. Assembling an electrolytic cell: the positive and negative polar plates are the positive and negative polar plates of the embodiment; the diaphragm is a diaphragm of a American celgard 2400 type battery; the positive and negative electrolyte is a mixed solution consisting of 2.5mol/L zinc bromide, 2.5mol/L sodium chloride and the balance of water. The specific assembly steps refer to the preparation of the diaphragm for the zinc-bromine flow battery and the performance research of the Sun Yu 'the preparation and performance research of the diaphragm for the zinc-bromine flow battery' the assembly of the single cell in the 2.4.5 academic paper of the professional university of the major graduates of 2015 university. And carrying out a charge-discharge cycle test at room temperature at 1C between 3.0V and 4.2V. And (3) testing results: after 500 cycles, the battery capacity was 96%.
Example 8
A zinc-bromine flow battery polar plate comprises a positive plate and a negative plate.
The positive plate is a zeolite imidazole ester framework structure nano carbon sheet graphite plate.
The negative plate is carbon cloth (from Shanghai Liong composite material science and technology Co., Ltd., length x width of 6cm x 6cm, specific gravity of 220 g/m)2)。
The preparation method of the zeolite imidazole ester framework structure nano carbon sheet graphite plate comprises the following steps:
s1, batching:
mixing petroleum coke and asphalt according to the mass ratio of 3:1, and kneading the mixture for 30min at the speed of 200r/min in an ZNH-5L kneader (New Hongda chemical machinery Co., Ltd. of Lyzhou) to form core slurry; adding the zeolite imidazole ester framework structure nano carbon sheet into a dispersing agent at 25 ℃, and ultrasonically dispersing for 30min to prepare a zeolite imidazole ester framework structure nano carbon sheet dispersion liquid with the concentration of 40 mg/mL; dispersing zeolite imidazole ester framework structure nano carbon sheet dispersion liquid, petroleum coke, asphalt, tungsten oxide carbon nano tubes, boron carbide micro powder and silicon carbide micro powder according to a mass ratio of 1: 10: 3: 0.5: 0.5: 0.5, mixing uniformly, kneading for 30min at 200r/min in an ZNH-5L kneader (Laizhou Xin Hongda chemical machinery Co., Ltd.) to form a surface sizing agent; the dispersant is N, N-dimethylformamide; the power of the ultrasonic dispersion is 300W, and the frequency is 40 KHz;
s2 blank forming:
a co-extrusion machine is adopted to match with the double-layer co-extrusion die orifice, so that the surface slurry is wrapped by the core slurry; then pressurizing, drying and shaping the raw materials together to form a composite green body; in the pressure drying and shaping, the extrusion temperature is controlled at 110 ℃, the extrusion pressure is controlled at 15MPa, and the pressure maintaining time is controlled for 10 min;
s3 graphitization treatment:
the composite green compact obtained in the step S2 is subjected to conventional roasting and graphitization high-temperature treatment, and then is cut to 6cm multiplied by 0.5cm (length multiplied by width multiplied by thickness), so that the zeolite imidazole ester framework structure nano carbon sheet graphite plate is obtained; the roasting temperature is controlled to be 1200 ℃, the roasting time is 22 days, the graphitization high-temperature treatment is controlled to be 2700 ℃, and the graphitization high-temperature treatment time is 18 hours.
Finally, obtaining a positive plate of the nano carbon sheet graphite plate with the material of zeolite imidazole ester framework structure, wherein the cross section of the positive plate is in a shape like Chinese character 'hui'; the outer layer is surface slurry, and the inner part is core slurry. The mass ratio of the core part slurry to the surface slurry is 10: 3.
the preparation method of the zeolite imidazole ester framework structure nano carbon sheet comprises the following steps:
a, dissolving 0.95g of zinc acetate in 260mL of water to obtain a zinc acetate aqueous solution; 2.9g of 2-methylimidazole is dissolved in 260mL of water to obtain a 2-methylimidazole aqueous solution; dropwise adding a 2-methylimidazole aqueous solution into a zinc acetate aqueous solution at the speed of 0.05g/s at the temperature of 25 ℃ and at the speed of 300r/min, continuously stirring for 24 hours at the temperature of 25 ℃ and at the speed of 300r/min after dropwise adding, filtering by using a 500-mesh gauze, respectively washing the obtained solid by using absolute ethyl alcohol and deionized water for 3 times, wherein the volume of the absolute ethyl alcohol or the deionized water after washing for each time is 50mL, and drying for 48 hours at the temperature of 40 ℃ to obtain the zeolite imidazolate framework structure material;
and B, heating the zeolite imidazole ester framework structure material from 25 ℃ to 900 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat at 900 ℃ for 2h, then heating from 900 ℃ to 1200 ℃ at a heating rate of 10 ℃/min in a carbon dioxide atmosphere, preserving heat at 1200 ℃ for 2h, and naturally cooling to room temperature to obtain the zeolite imidazole ester framework structure nano-carbon sheet.
Assembling an electrolytic cell: the positive and negative polar plates are the positive and negative polar plates of the embodiment; the diaphragm is a diaphragm of a American celgard 2400 type battery; the positive and negative electrolyte is a mixed solution consisting of 2.5mol/L zinc bromide, 2.5mol/L sodium chloride and the balance of water. The specific assembly steps refer to the preparation of the diaphragm for the zinc-bromine flow battery and the performance research of the Sun Yu 'the preparation and performance research of the diaphragm for the zinc-bromine flow battery' the assembly of the single cell in the 2.4.5 academic paper of the professional university of the major graduates of 2015 university. And carrying out a charge-discharge cycle test at room temperature at 1C between 3.0V and 4.2V. And (3) testing results: after 500 cycles, the battery capacity was 93%.
In the examples, the raw materials of each part are as follows:
petroleum coke: low sulfur coke content of less than or equal to 2.0 percent, granularity of 100 meshes, Shandong Chenxuan novel carbon materials Co.
Asphalt: NORMIC/Nomke, softening point 85 ℃, Kunning Bai chemical Co.
Preparing tungsten oxide carbon nanotubes: ultrasonically dispersing 1.0g of carbon nano tube in 40mL of mixed solution of concentrated nitric acid and concentrated sulfuric acid (30mL of mixed solution of concentrated nitric acid with the mass fraction of 65% and 10mL of concentrated sulfuric acid with the mass fraction of 98%) for 30min to obtain dispersion liquid; the ultrasonic power is 350W, and the frequency is 40 KHz; refluxing the dispersion liquid for 3h under 140 ℃ oil bath, performing centrifugal separation under 10000 r/min, washing the obtained precipitate with deionized water for 3 times, wherein the amount of the deionized water is 30mL each time, and drying the obtained precipitate for 24h under 60 ℃ conventional vacuum condition to obtain an acidified carbon nano tube; adding 5.0g of acidified carbon nano tube into an ammonium metatungstate aqueous solution with the mass fraction of 15%, stirring for 4 hours in a water bath at 60 ℃ under the condition of 500 revolutions per minute, and drying the filtered solid for 6 hours at 80 ℃; and (3) putting the obtained solid in a tube furnace, heating the solid from 25 ℃ to 550 ℃ at the heating rate of 5 ℃/min, preserving the heat at 550 ℃ for 4h, and naturally cooling to room temperature to obtain the tungsten oxide carbon nano tube.
Boron carbide micro powder: 250 meshes in granularity, more than or equal to 80 percent in boron content, and the Nangong Jingding alloy material Co.
Silicon carbide micro powder: 320 meshes in granularity, and is produced in big gang grinding wheel II factory in salt city.
Zinc acetate: CAS number: 557-34-6.
2-methylimidazole: CAS number: 693-98-1.
Test example 1
The performance test method comprises the following steps:
(1) and (3) resistivity testing: the positive plates obtained in examples 1 to 6 were subjected to resistivity test by referring to the direct current probe drop method specified in GB6717-86 "method for measuring resistivity of carbon material".
(2) And (3) bromine soaking deformation testing:
a, fixing the graphite plate with the zeolite imidazole ester framework structure nano carbon sheet with the length multiplied by 6cm multiplied by 0.5cm (length multiplied by width multiplied by thickness) obtained in the embodiments 1 to 6 by using a frame, wherein the surface of the graphite plate is required to be smooth, clean, free of cracks, free of defects such as bubbles and impurities, free of stretching or bending, and free of polishing or grinding;
b, putting the mixture into a mixed aqueous solution of 2.5mol/L zinc bromide and 2.5mol/L bromine, maintaining the temperature at 50 ℃, and soaking for one week;
c, taking out the soaked sample, washing the sample with clear water, and airing the sample to be tested;
and d, measuring the deformation of the soaked sample in the thickness direction by using a height gauge and a finishing carving machine tool to obtain the maximum deformation value (mm).
Comparative graphite electrodes were purchased from the market (Zibo Zheng carbon Co., Ltd.) and were cut to 6 cm. times.6 cm. times.0.5 cm (length. times.width. times.thickness) according to the test requirements.
TABLE 1 resistivity and maximum bromine dip deformation
| Examples | Resistivity/μ Ω · cm | Maximum bromine dip deformation/mm |
| Reference graphite electrode | 8.5 | 4.7 |
| Example 1 | 6.3 | 4.2 |
| Example 2 | 4.7 | 3.6 |
| Example 3 | 3.8 | 2.6 |
| Example 4 | 4.0 | 2.7 |
| Example 5 | 4.4 | 3.2 |
| Example 6 | 3.0 | 2.2 |
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (7)
1. The utility model provides a zinc bromine redox flow battery polar plate, includes positive plate and negative plate, its characterized in that: the positive plate is a zeolite imidazole ester framework structure nano carbon sheet graphite plate; the negative plate is one of a graphite plate, a carbon felt, a graphite felt or a carbon cloth;
the preparation method of the zeolite imidazole ester framework structure nano carbon sheet graphite plate comprises the following steps:
s1, batching:
kneading petroleum coke and asphalt to form a core slurry; adding the zeolite imidazole ester framework structure nano carbon sheet into a dispersing agent at the temperature of 10-35 ℃, and ultrasonically dispersing for 10-30 min to prepare a zeolite imidazole ester framework structure nano carbon sheet dispersion liquid with the concentration of 20-50 mg/mL; kneading zeolite imidazole ester framework structure nano carbon sheet dispersion liquid, petroleum coke, asphalt and reinforced particles to form surface sizing agent;
s2 blank forming:
a co-extrusion machine is adopted to match with the double-layer co-extrusion die orifice, so that the surface slurry is wrapped by the core slurry; then pressurizing, drying and shaping the raw materials together to form a composite green body; in the pressure drying and shaping, the extrusion temperature is controlled to be 105-125 ℃, the extrusion pressure is controlled to be 10-18 MPa, and the pressure maintaining time is controlled to be 5-10 min;
s3 graphitization treatment:
the composite green compact obtained in the step S2 is subjected to conventional roasting and graphitization high-temperature treatment, and then is cut into a required shape according to production requirements, so that the zeolite imidazole ester framework structure nano carbon sheet graphite plate is obtained; the roasting temperature is controlled to be 1000-1250 ℃, the roasting time is 10-30 days, the graphitization high-temperature treatment is controlled to be 2700-3400 ℃, and the graphitization high-temperature treatment time is 15-50 hours;
the preparation method of the zeolite imidazole ester framework structure nano carbon sheet comprises the following steps:
a, dissolving 0.9-1.1 g of zinc acetate in 250-300 mL of water to obtain a zinc acetate aqueous solution; dissolving 2.8-3.2 g of 2-methylimidazole in 250-300 mL of water to obtain a 2-methylimidazole water solution; dropwise adding a 2-methylimidazole water solution into a zinc acetate water solution at the speed of 0.02-0.05 g/s at the temperature of 10-35 ℃ at 200-500 r/min, continuously stirring for 20-36 hours at the temperature of 10-35 ℃ at 200-500 r/min after dropwise adding, filtering, washing, and drying for 24-48 hours at the temperature of 40-60 ℃ to obtain a zeolite imidazole ester framework material;
and B, heating the zeolite imidazole ester framework structure material from 10-35 ℃ to 800-1000 ℃ at a heating rate of 3-5 ℃/min in a nitrogen atmosphere, preserving heat at 800-1000 ℃ for 1-3 h, then heating from 800-1000 ℃ to 1200-1400 ℃ at a heating rate of 5-10 ℃/min in a carbon dioxide atmosphere, preserving heat at 1200-1400 ℃ for 1.5-3 h, and naturally cooling to room temperature to obtain the zeolite imidazole ester framework structure nano carbon sheet.
2. The zinc-bromine flow battery plate of claim 1, wherein: the mass ratio of the petroleum coke to the asphalt in the core slurry is (3-6) to (1-3).
3. The zinc-bromine flow battery plate of claim 1, wherein: the mass ratio of zeolite imidazole ester framework structure nano carbon sheet dispersion liquid, petroleum coke, asphalt and reinforcing particles in the surface sizing agent is 1 (10-15): (3-5): 1-2.
4. The zinc-bromine flow battery plate of claim 3, wherein: the reinforced particles are tungsten oxide carbon nano tubes, boron carbide micro powder and silicon carbide micro powder according to the mass ratio of 1: 1: 1 are mixed.
5. The zinc-bromine flow battery plate of claim 1, wherein: the mass ratio of the core part slurry to the surface slurry is 10 (2-5).
6. The zinc-bromine flow battery plate of claim 1, wherein: the dispersing agent is one or more of absolute ethyl alcohol, N-dimethylformamide and tetrahydrofuran.
7. The zinc-bromine flow battery plate of claim 1, wherein: the power of ultrasonic dispersion in the step S1 is 150-300W, and the frequency is 24-40 KHz.
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