CN108400365A - zinc-bromine flow battery - Google Patents
zinc-bromine flow battery Download PDFInfo
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- CN108400365A CN108400365A CN201810172461.5A CN201810172461A CN108400365A CN 108400365 A CN108400365 A CN 108400365A CN 201810172461 A CN201810172461 A CN 201810172461A CN 108400365 A CN108400365 A CN 108400365A
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- polyacrylonitrile
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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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- 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
- Y02E60/10—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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a kind of zinc-bromine flow batteries, including positive plate, negative plate and the battery diaphragm being arranged between the positive plate and negative plate；The positive plate is preferably one kind in graphite cake, carbon felt, graphite felt or carbon cloth；The negative plate is preferably one kind in graphite cake, carbon felt, graphite felt or carbon cloth；The battery diaphragm is single layer PE, PP film, 3 layers of PP, PE film or polyacrylonitrile basement membrane.Zinc-bromine flow battery prepared by the present invention, the longitudinal tensile strength of battery diaphragm is in 168MPa or more, and percent thermal shrinkage is 1.2% hereinafter, having excellent mechanical performance.The zinc-bromine flow battery of the present invention, can large capacity, prolonged charge and discharge, efficiency for charge-discharge is high.
Description
Technical field
The present invention relates to a kind of battery more particularly to a kind of zinc-bromine flow batteries.
Background technology
Zinc-bromine flow battery is a kind of electrochemical energy storage new technology, compared with other energy storage technologies, has energy conversion effect
Rate height, system flexible design, capacitance of storage is big, addressing is free, can the advantages such as deep discharge, safety and environmental protection, maintenance cost be low, can
It is cut with being widely used in the energy storage of the renewable energy power generations such as wind energy, solar energy, emergency power system, stand-by station and electric system
Peak load etc..
Zinc-bromine flow battery is a kind of liquid flow energy storage battery.Diaphragm is the important component in zinc-bromine flow battery, it
Barrier positive and negative electrode electrolyte is played, the effect of proton transmitting channel is provided.Proton-conducting, chemical stability and the ion of film
Selectivity etc. will directly affect the chemical property and service life of battery；Therefore it is required that film is permeated with lower active material
Rate (having higher selectivity) and lower surface resistance (having higher ionic conductivity), while should also have preferableization
Learn stability and lower cost.Diaphragm in battery can influence the service efficiency of battery.Electrolyte cost in battery is almost
Flow battery totle drilling cost 30% can be accounted for, so the price decision of the electrolyte overall cost of battery.Zinc-bromine flow battery because
For the high-energy density of zinc, low price and be easy it is a large amount of obtain, so the system containing zinc can charge-discharge battery storing up on a large scale
Energy system has very strong competitiveness.This electrolyte characteristic determines zinc-bromine flow battery in terms of cost with prodigious excellent
Gesture.Zinc-bromine flow battery electric discharge inch, the metallic zinc of surface deposition can be completely dissolved in the electrolytic solution, deep to continually carry out
Charge and discharge are spent, without causing battery loss.
Zinc-bromine flow battery diaphragm is in developmental research it should be noted that the performance of following aspect.First, in physical chemistry
Aspect, zinc-bromine flow battery need have smaller swelling ratio with diaphragm, ensure there is good mechanical strength, respectively to uniform, have
Enough tensile stress also have certain flexibility and toughness, to reduce the installation the problem of, ease of assembly and tear open
It unloads.Secondly, in terms of electrochemistry, diaphragm needs have higher conductivity and stronger ion selectivity, in this way can be effective
Battery efficiency is improved, the percent of pass of simple substance bromine is reduced, positive and negative anodes electrolyte is preferably isolated, prevents self-discharge of battery, raising from making
Use efficiency.Finally, diaphragm must have highly-acidproof, high oxidation resistance and stablize electrochemistry.
Invention content
In view of the drawbacks described above of the prior art, technical problem to be solved by the invention is to provide a kind of zinc bromine liquid stream electricity
Pond.
A kind of zinc-bromine flow battery, including positive plate, negative plate and be arranged between the positive plate and negative plate
Battery diaphragm；
The positive plate is metal class, such as Pb, Ti etc.；Charcoal element class, such as graphite, carbon cloth, carbon felt；Composite material class, such as
Conducting polymer, polymer composite etc., the positive plate are preferably one in graphite cake, carbon felt, graphite felt or carbon cloth
Kind；
The negative plate is metal class, such as Pb, Ti etc.；Charcoal element class, such as graphite, carbon cloth, carbon felt；Composite material class, such as
Conducting polymer, polymer composite etc., the negative plate are preferably one in graphite cake, carbon felt, graphite felt or carbon cloth
Kind；
The battery diaphragm is composite material class, such as conducting polymer, polymer composite, preferably single layer PE,
PP films, 3 layers of PP, PE film, Nafion membrane or polyacrylonitrile basement membrane, the battery diaphragm are preferably polyacrylonitrile battery diaphragm.
Nafion diaphragms are perfluorinated sulfonic acid diaphragm, English name：Nafion nr 50 (beads10-35mesh), CAS
Number：31175-20-9.
It is further preferred that the polyacrylonitrile battery diaphragm is prepared using following methods：
High molecular polymer is dissolved in organic solvent by S1, obtain high molecular polymer mass fraction be 10~15% it is molten
Liquid A；
Stabilizer, polyacrylonitrile, polyvinylpyrrolidone are added in n,N-dimethylacetamide by S2, obtain solution
B；
S3 scratches solution B on a glass, stands, and forms film；Film is put into together with glass plate in solidification liquid and is soaked
Stain；It tears film, rinses, it is dry, obtain polyacrylonitrile basement membrane；
Solution A is coated on polyacrylonitrile basement membrane by S4, is dried to get the polyacrylonitrile battery diaphragm.
Preferably, the polyacrylonitrile battery diaphragm is prepared using following methods：
High molecular polymer is dissolved in organic solvent by S1, obtain high molecular polymer mass fraction be 10~15% it is molten
Liquid A；
The high molecular polymer is polybenzimidazoles and/or perfluorinated sulfonic acid polymer；Preferably, the high molecular polymerization
Polybenzimidazoles accounts for 25~35wt% in object, and perfluorinated sulfonic acid polymer accounts for 65~75wt%.It is further preferred that the macromolecule
Polybenzimidazoles accounts for 30wt% in polymer, and perfluorinated sulfonic acid polymer accounts for 70wt%；
Preferably, in the step S1 organic solvent be dimethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO),
One kind in N,N-dimethylformamide, DMAC N,N' dimethyl acetamide；
Stabilizer, polyacrylonitrile, polyvinylpyrrolidone are added in n,N-dimethylacetamide by S2,60~80
20~30h is stirred with the rotating speed of 300~500r/min at DEG C, 20~30h of standing is protected from light, obtains solution B；
Preferably, the stabilizer, polyacrylonitrile, polyvinylpyrrolidone, n,N-dimethylacetamide mass ratio be
(0.5~0.8)：(10~15)：(1~3)：(70~85)；
S3 uniformly scratches solution B on clean glass plate, blade coating finish after be exposed to temperature for 35~50 DEG C,
5~10min is stood under conditions of humidity 70~90%, forms film；Then film is immersed together with glass plate in solidification liquid and is soaked
60~80s of stain；It tears film, is rinsed with water, 4~8h is dried in vacuo at 60~80 DEG C, obtains polyacrylonitrile basement membrane；
The thickness control of the polyacrylonitrile basement membrane is between 50~80 μm；
Solution A is coated on polyacrylonitrile basement membrane by S4,1.5~3h is dried at 50~70 DEG C, then in 75~90 DEG C of water
Then 10~15h of middle immersion is dried in vacuo 6~10h to get the polyacrylonitrile battery diaphragm at 40~60 DEG C；It is described molten
The dosage of liquid A is that polyacrylonitrile basement membrane every square centimeter coats 40~60 μ L solution As.
Preferably, in the step S3 solidification liquid by n,N-dimethylacetamide and water by volume (2~5)：20 mixing
It forms.
Currently, battery diaphragm common in the art is thin polymer film, simple thin polymer film thermal stability is poor,
Mechanical strength is low, and being easy swelling after long-term use reduces the service efficiency of battery.The present invention in thin polymer film by adding
Add stabilizer, hole is prepared and more enriches, while the diaphragm that mechanical strength is more excellent so that diaphragm has excellent conductance
Rate can be used for a long time without damaging.
Preferably, the stabilizer is montmorillonite and/or silica.
It is further preferred that the stabilizer is organo montmorillonite and/or silica.
As one of which preferred embodiment, the stabilizer is organo montmorillonite and silica (3~5) in mass ratio：1
It mixes.
Preferably, the preparation method of the organo montmorillonite is：1~3g montmorillonite powder is dispersed in 30~50mL water
40~80min is stirred with the rotating speed of 300~500r/min at 45~60 DEG C, obtains montmorillonite dispersions；By 0.7~1.1g 16
Alkyl trimethyl ammonium bromide be added to 8~12mL temperature be rotating speed stirring 5 in 80~90 DEG C of water with 100~300r/min~
10min obtains cetyl trimethylammonium bromide aqueous solution；In the case where rotating speed is the stirring of 100~300r/min by cetyl
Trimethylammonium bromide aqueous solution is dropped to the speed of 0.05~0.1g/s in montmorillonite dispersions, after being added dropwise continue with
The rotating speed of 100~300r/min stirs 5~8h, filters, through water washing to not bromine ion-containing, obtained solid exists obtained solid
It is dried in vacuo 20~30h at 70~90 DEG C, pulverizes up to organo montmorillonite.
Beneficial effects of the present invention：
The longitudinal tensile strength of zinc-bromine flow battery prepared by the present invention, battery diaphragm is heat-shrinked in 168MPa or more
Rate is 1.2% hereinafter, having excellent mechanical performance.The zinc-bromine flow battery of the present invention, being capable of large capacity, prolonged charge and discharge
Electricity, efficiency for charge-discharge are high.Moreover, battery diaphragm of the invention is also equipped with higher conductivity.Conductivity is higher, and resistance is got over
It is small, illustrate that the obstruction ability that diaphragm flows electronics is smaller, the chemical property of diaphragm is more excellent.
Specific implementation mode
With reference to specific embodiment, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention, after having read the present invention, various equivalences of the those skilled in the art to the present invention
The modification of form falls within the application range as defined in the appended claims.
Embodiment 1
Perfluorinated sulfonic acid polymer is dissolved in N-Methyl pyrrolidone by S1, is obtained perfluorinated sulfonic acid polymer mass fraction and is
12% solution A；
Stabilizer, polyacrylonitrile, polyvinylpyrrolidone are added in DMAC N,N' dimethyl acetamide at 70 DEG C by S2
For 24 hours with the rotating speed stirring of 500r/min, standing is protected from light for 24 hours to eliminate bubble, obtains solution B；The stabilizer, polyacrylonitrile,
Polyvinylpyrrolidone, DMAC N,N' dimethyl acetamide mass ratio be 0.6：14：2：84；
S3 uniformly scratches solution B on clean glass plate, and blade coating is exposed to temperature after finishing be 50 DEG C, humidity
10min is stood under conditions of 90%, forms film；Then film is put into dipping 60s in solidification liquid together with glass plate (ensures to coagulate
Solid-liquid can flood glass plate and film)；It tears film, is rinsed with deionized water, 5h is dried in vacuo at 70 DEG C, obtain poly- third
Alkene itrile group film；The thickness control of polyacrylonitrile basement membrane is at 70 μm；The solidification liquid is by DMAC N,N' dimethyl acetamide and deionized water
By volume 3：20 mix.
Solution A is coated on polyacrylonitrile basement membrane by S4, and 2h is dried at 60 DEG C, is then impregnated in 80 DEG C of deionized water
Then 12h is dried in vacuo 10h to get polyacrylonitrile battery diaphragm at 40 DEG C；The dosage of the solution A is every square centimeter
Polyacrylonitrile basement membrane coat 50 μ L solution As.
The stabilizer is organo montmorillonite.
The preparation method of the organo montmorillonite is：2g montmorillonite powder is dispersed in 40mL water at 50 DEG C with 300r/
The rotating speed of min stirs 60min, obtains montmorillonite dispersions；0.8g cetyl trimethylammonium bromides are added to 10mL temperature
To stir 10min in 90 DEG C of water with the rotating speed of 200r/min, cetyl trimethylammonium bromide aqueous solution is obtained；It is in rotating speed
Cetyl trimethylammonium bromide aqueous solution at a temperature of 90 °C is dropped into temperature with the speed of 0.05g/s under the stirring of 300r/min
Degree is to stir 6h, conventional filter paper under 50 DEG C of water-baths with the rotating speed of 300r/min after being added dropwise in 50 DEG C of montmorillonite dispersions
It filters, obtained solid is washed through deionized water to not bromine ion-containing (silver nitrate detection), and obtained solid is in 80 DEG C, vacuum
Degree is that drying for 24 hours, is pulverized up to organo montmorillonite under 0.02MPa.
Embodiment 2
Polybenzimidazoles is dissolved in N-Methyl pyrrolidone by S1, obtains the solution that polybenzimidazoles mass fraction is 12%
A；
Stabilizer, polyacrylonitrile, polyvinylpyrrolidone are added in DMAC N,N' dimethyl acetamide at 70 DEG C by S2
For 24 hours with the rotating speed stirring of 500r/min, standing is protected from light for 24 hours to eliminate bubble, obtains solution B；The stabilizer, polyacrylonitrile,
Polyvinylpyrrolidone, DMAC N,N' dimethyl acetamide mass ratio be 0.6：14：2：84；
S3 uniformly scratches solution B on clean glass plate, and blade coating is exposed to temperature after finishing be 50 DEG C, humidity
10min is stood under conditions of 90%, forms film；Then film is put into dipping 60s in solidification liquid together with glass plate (ensures to solidify
Liquid energy floods glass plate and film)；It tears film, is rinsed with deionized water, be dried in vacuo 5h at 70 DEG C, obtain polypropylene
Itrile group film；The thickness control of polyacrylonitrile basement membrane is at 70 μm；The solidification liquid is pressed by DMAC N,N' dimethyl acetamide and deionized water
Volume ratio 3：20 mix.
Solution A is coated on polyacrylonitrile basement membrane by S4, and 2h is dried at 60 DEG C, is then impregnated in 80 DEG C of deionized water
Then 12h is dried in vacuo 10h to get polyacrylonitrile battery diaphragm at 40 DEG C；The dosage of the solution A is every square centimeter
Polyacrylonitrile basement membrane coat 50 μ L solution As.
The stabilizer is silica.
Embodiment 3
Perfluorinated sulfonic acid polymer is dissolved in N-Methyl pyrrolidone by S1, is obtained perfluorinated sulfonic acid polymer mass fraction and is
12% solution A；
Stabilizer, polyacrylonitrile, polyvinylpyrrolidone are added in DMAC N,N' dimethyl acetamide at 70 DEG C by S2
For 24 hours with the rotating speed stirring of 500r/min, standing is protected from light for 24 hours to eliminate bubble, obtains solution B；The stabilizer, polyacrylonitrile,
Polyvinylpyrrolidone, DMAC N,N' dimethyl acetamide mass ratio be 0.6：14：2：84；
S3 uniformly scratches solution B on clean glass plate, and blade coating is exposed to temperature after finishing be 50 DEG C, humidity
10min is stood under conditions of 90%, forms film；Then film is put into dipping 60s in solidification liquid together with glass plate (ensures to coagulate
Solid-liquid can flood glass plate and film)；It tears film, is rinsed with deionized water, 5h is dried in vacuo at 70 DEG C, obtain poly- third
Alkene itrile group film；The thickness control of polyacrylonitrile basement membrane is at 70 μm；The solidification liquid is by DMAC N,N' dimethyl acetamide and deionized water
By volume 3：20 mix.
Solution A is coated on polyacrylonitrile basement membrane by S4, and 2h is dried at 60 DEG C, is then impregnated in 80 DEG C of deionized water
Then 12h is dried in vacuo 10h to get polyacrylonitrile battery diaphragm at 40 DEG C；The dosage of the solution A is every square centimeter
Polyacrylonitrile basement membrane coat 50 μ L solution As.
The stabilizer is silica.
Embodiment 4
High molecular polymer is dissolved in N-Methyl pyrrolidone by S1, and it is 12% to obtain high molecular polymer mass fraction
Solution A；Polybenzimidazoles accounts for 30wt% in the high molecular polymer, and perfluorinated sulfonic acid polymer accounts for 70wt%；
Stabilizer, polyacrylonitrile, polyvinylpyrrolidone are added in DMAC N,N' dimethyl acetamide at 70 DEG C by S2
For 24 hours with the rotating speed stirring of 500r/min, standing is protected from light for 24 hours to eliminate bubble, obtains solution B；The stabilizer, polyacrylonitrile,
Polyvinylpyrrolidone, DMAC N,N' dimethyl acetamide mass ratio be 0.6：14：2：84；
S3 uniformly scratches solution B on clean glass plate, and blade coating is exposed to temperature after finishing be 50 DEG C, humidity
10min is stood under conditions of 90%, forms film；Then film is put into dipping 60s in solidification liquid together with glass plate (ensures to coagulate
Solid-liquid can flood glass plate and film)；It tears film, is rinsed with deionized water, 5h is dried in vacuo at 70 DEG C, obtain poly- third
Alkene itrile group film；The thickness control of polyacrylonitrile basement membrane is at 70 μm；The solidification liquid is by DMAC N,N' dimethyl acetamide and deionized water
By volume 3：20 mix.
Solution A is coated on polyacrylonitrile basement membrane by S4, and 2h is dried at 60 DEG C, is then impregnated in 80 DEG C of deionized water
Then 12h is dried in vacuo 10h to get polyacrylonitrile battery diaphragm at 40 DEG C；The dosage of the solution A is every square centimeter
Polyacrylonitrile basement membrane coat 50 μ L solution As.
The stabilizer is silica.
Comparative example 1
High molecular polymer is dissolved in N-Methyl pyrrolidone by S1, and it is 12% to obtain high molecular polymer mass fraction
Solution A；Polybenzimidazoles accounts for 30wt% in the high molecular polymer, and perfluorinated sulfonic acid polymer accounts for 70wt%；
Polyacrylonitrile, polyvinylpyrrolidone are added in DMAC N,N' dimethyl acetamide at 70 DEG C with 500r/ by S2
The rotating speed stirring of min for 24 hours, is protected from light standing for 24 hours to eliminate bubble, obtains solution B；The polyacrylonitrile, polyvinylpyrrolidone,
The mass ratio of DMAC N,N' dimethyl acetamide is 7：1：42；
S3 uniformly scratches solution B on clean glass plate, and blade coating is exposed to temperature after finishing be 50 DEG C, humidity
10min is stood under conditions of 90%, forms film；Then film is put into dipping 60s in solidification liquid together with glass plate (ensures to coagulate
Solid-liquid can flood glass plate and film)；It tears film, is rinsed with deionized water, 5h is dried in vacuo at 70 DEG C, obtain poly- third
Alkene itrile group film；The thickness control of polyacrylonitrile basement membrane is at 70 μm；The solidification liquid is by DMAC N,N' dimethyl acetamide and deionized water
By volume 3：20 mix.
Solution A is coated on polyacrylonitrile basement membrane by S4, and 2h is dried at 60 DEG C, is then impregnated in 80 DEG C of deionized water
Then 12h is dried in vacuo 10h to get polyacrylonitrile battery diaphragm at 40 DEG C；The dosage of the solution A is every square centimeter
Polyacrylonitrile basement membrane coat 50 μ L solution As.
Embodiment 5
High molecular polymer is dissolved in N-Methyl pyrrolidone by S1, and it is 12% to obtain high molecular polymer mass fraction
Solution A；Polybenzimidazoles accounts for 30wt% in the high molecular polymer, and perfluorinated sulfonic acid polymer accounts for 70wt%；
Stabilizer, polyacrylonitrile, polyvinylpyrrolidone are added in DMAC N,N' dimethyl acetamide at 70 DEG C by S2
For 24 hours with the rotating speed stirring of 500r/min, standing is protected from light for 24 hours to eliminate bubble, obtains solution B；The stabilizer, polyacrylonitrile,
Polyvinylpyrrolidone, DMAC N,N' dimethyl acetamide mass ratio be 0.6：14：2：84；
S3 uniformly scratches solution B on clean glass plate, and blade coating is exposed to temperature after finishing be 50 DEG C, humidity
10min is stood under conditions of 90%, forms film；Then film is put into dipping 60s in solidification liquid together with glass plate (ensures to coagulate
Solid-liquid can flood glass plate and film)；It tears film, is rinsed with deionized water, 5h is dried in vacuo at 70 DEG C, obtain poly- third
Alkene itrile group film；The thickness control of polyacrylonitrile basement membrane is at 70 μm；The solidification liquid is by DMAC N,N' dimethyl acetamide and deionized water
By volume 3：20 mix.
S4 coats solution A on polyacrylonitrile basement membrane, and 2h is dried at 60 DEG C, then impregnates 12h in 80 DEG C of deionized water,
Then 10h is dried in vacuo at 40 DEG C to get polyacrylonitrile battery diaphragm；The dosage of the solution A is every square centimeter gathers
Acrylonitrile basement membrane coats 50 μ L solution As.
The stabilizer is montmorillonite.
Embodiment 6
High molecular polymer is dissolved in N-Methyl pyrrolidone by S1, and it is 12% to obtain high molecular polymer mass fraction
Solution A；Polybenzimidazoles accounts for 30wt% in the high molecular polymer, and perfluorinated sulfonic acid polymer accounts for 70wt%；
Stabilizer, polyacrylonitrile, polyvinylpyrrolidone are added in DMAC N,N' dimethyl acetamide at 70 DEG C by S2
For 24 hours with the rotating speed stirring of 500r/min, standing is protected from light for 24 hours to eliminate bubble, obtains solution B；The stabilizer, polyacrylonitrile,
Polyvinylpyrrolidone, DMAC N,N' dimethyl acetamide mass ratio be 0.6：14：2：84；
S3 uniformly scratches solution B on clean glass plate, and blade coating is exposed to temperature after finishing be 50 DEG C, humidity
10min is stood under conditions of 90%, forms film；Then film is put into dipping 60s in solidification liquid together with glass plate (ensures to solidify
Liquid energy floods glass plate and film)；It tears film, is rinsed with deionized water, be dried in vacuo 5h at 70 DEG C, obtain polypropylene
Itrile group film；The thickness control of polyacrylonitrile basement membrane is at 70 μm；The solidification liquid is pressed by DMAC N,N' dimethyl acetamide and deionized water
Volume ratio 3：20 mix.
Solution A is coated on polyacrylonitrile basement membrane by S4, and 2h is dried at 60 DEG C, is then impregnated in 80 DEG C of deionized water
Then 12h is dried in vacuo 10h to get polyacrylonitrile battery diaphragm at 40 DEG C；The dosage of the solution A is every square centimeter
Polyacrylonitrile basement membrane coat 50 μ L solution As.
The stabilizer is organo montmorillonite.
The preparation method of the organo montmorillonite is：2g montmorillonite powder is dispersed in 40mL water at 50 DEG C with 300r/
The rotating speed of min stirs 60min, obtains montmorillonite dispersions；0.8g cetyl trimethylammonium bromides are added to 10mL temperature
To stir 10min in 90 DEG C of water with the rotating speed of 200r/min, cetyl trimethylammonium bromide aqueous solution is obtained；It is in rotating speed
Cetyl trimethylammonium bromide aqueous solution at a temperature of 90 °C is dropped into temperature with the speed of 0.05g/s under the stirring of 300r/min
Degree is to stir 6h, conventional filter paper under 50 DEG C of water-baths with the rotating speed of 300r/min after being added dropwise in 50 DEG C of montmorillonite dispersions
It filters, obtained solid is washed through deionized water to not bromine ion-containing (silver nitrate detection), and obtained solid is in 80 DEG C, vacuum
Degree is that drying for 24 hours, is pulverized up to organo montmorillonite under 0.02MPa.
Embodiment 7
High molecular polymer is dissolved in N-Methyl pyrrolidone by S1, and it is 12% to obtain high molecular polymer mass fraction
Solution A；Polybenzimidazoles accounts for 30wt% in the high molecular polymer, and perfluorinated sulfonic acid polymer accounts for 70wt%；
Stabilizer, polyacrylonitrile, polyvinylpyrrolidone are added in DMAC N,N' dimethyl acetamide at 70 DEG C by S2
For 24 hours with the rotating speed stirring of 500r/min, standing is protected from light for 24 hours to eliminate bubble, obtains solution B；The stabilizer, polyacrylonitrile,
Polyvinylpyrrolidone, DMAC N,N' dimethyl acetamide mass ratio be 0.6：14：2：84；
S3 uniformly scratches solution B on clean glass plate, and blade coating is exposed to temperature after finishing be 50 DEG C, humidity
10min is stood under conditions of 90%, forms film；Then film is put into dipping 60s in solidification liquid together with glass plate (ensures to solidify
Liquid energy floods glass plate and film)；It tears film, is rinsed with deionized water, be dried in vacuo 5h at 70 DEG C, obtain polypropylene
Itrile group film；The thickness control of polyacrylonitrile basement membrane is at 70 μm；The solidification liquid is pressed by DMAC N,N' dimethyl acetamide and deionized water
Volume ratio 3：20 mix.
Solution A is coated on polyacrylonitrile basement membrane by S4, and 2h is dried at 60 DEG C, is then impregnated in 80 DEG C of deionized water
Then 12h is dried in vacuo 10h to get polyacrylonitrile battery diaphragm at 40 DEG C；The dosage of the solution A is every square centimeter
Polyacrylonitrile basement membrane coat 50 μ L solution As.
The stabilizer is organo montmorillonite and silica in mass ratio 5：1.
The preparation method of the organo montmorillonite is：2g montmorillonite powder is dispersed in 40mL water at 50 DEG C with 300r/
The rotating speed of min stirs 60min, obtains montmorillonite dispersions；0.8g cetyl trimethylammonium bromides are added to 10mL temperature
To stir 10min in 90 DEG C of water with the rotating speed of 200r/min, cetyl trimethylammonium bromide aqueous solution is obtained；It is in rotating speed
Cetyl trimethylammonium bromide aqueous solution at a temperature of 90 °C is dropped into temperature with the speed of 0.05g/s under the stirring of 300r/min
Degree is to stir 6h, conventional filter paper under 50 DEG C of water-baths with the rotating speed of 300r/min after being added dropwise in 50 DEG C of montmorillonite dispersions
It filters, obtained solid is washed through deionized water to not bromine ion-containing (silver nitrate detection), and obtained solid is in 80 DEG C, vacuum
Degree is that drying for 24 hours, is pulverized up to organo montmorillonite under 0.02MPa.
Embodiment 8
High molecular polymer is dissolved in N-Methyl pyrrolidone by S1, and it is 12% to obtain high molecular polymer mass fraction
Solution A；Polybenzimidazoles accounts for 30wt% in the high molecular polymer, and perfluorinated sulfonic acid polymer accounts for 70wt%；
Stabilizer, polyacrylonitrile, polyvinylpyrrolidone are added in DMAC N,N' dimethyl acetamide at 70 DEG C by S2
For 24 hours with the rotating speed stirring of 500r/min, standing is protected from light for 24 hours to eliminate bubble, obtains solution B；The stabilizer, polyacrylonitrile,
Polyvinylpyrrolidone, DMAC N,N' dimethyl acetamide mass ratio be 0.6：14：2：84；
S3 uniformly scratches solution B on clean glass plate, and blade coating is exposed to temperature after finishing be 50 DEG C, humidity
10min is stood under conditions of 90%, forms film；Then film is put into dipping 60s in solidification liquid together with glass plate (ensures to solidify
Liquid energy floods glass plate and film)；It tears film, is rinsed with deionized water, be dried in vacuo 5h at 70 DEG C, obtain polypropylene
Itrile group film；The thickness control of polyacrylonitrile basement membrane is at 70 μm；The solidification liquid is pressed by DMAC N,N' dimethyl acetamide and deionized water
Volume ratio 3：20 mix.
Solution A is coated on polyacrylonitrile basement membrane by S4, and 2h is dried at 60 DEG C, is then impregnated in 80 DEG C of deionized water
Then 12h is dried in vacuo 10h to get polyacrylonitrile battery diaphragm at 40 DEG C；The dosage of the solution A is every square centimeter
Polyacrylonitrile basement membrane coat 50 μ L solution As.
The stabilizer is montmorillonite and silica in mass ratio 5：1.
Test case 1
The test of tensile strength：
With reference to《The measurement third portion of GB/T 1040.3-2006 plastic tensile performances：The experimental condition of film and thin slice》
Specified in specimen size the obtained polyacrylonitrile battery diaphragm of embodiment 2~8 and comparative example 1 is cut and is drawn
Stretch the test of intensity.
Percent thermal shrinkage is tested：The obtained polyacrylonitrile battery diaphragm of embodiment 2~8 and comparative example 1 is cut into diameter
Then the disk of 19mm heats 1 hour in 150 DEG C of baking oven respectively, then take out film and measure diameter, calculate percent thermal shrinkage.
The mechanical performance of diaphragm is as shown in table 1.
Table 1：The mechanical performance table of diaphragm
| Embodiment | Longitudinal tensile strength (MPa) | Percent thermal shrinkage (%) |
| Embodiment 2 | 174 | 1.5 |
| Embodiment 3 | 168 | 1.6 |
| Embodiment 4 | 184 | 1.2 |
| Comparative example 1 | 123 | 3.8 |
| Embodiment 5 | 181 | 1.4 |
| Embodiment 6 | 204 | 0.9 |
| Embodiment 7 | 226 | 0.4 |
| Embodiment 8 | 208 | 0.8 |
Test case 2
Test reference Sun Yu " preparation of zinc-bromine flow battery diaphragm and performance study " 2015 Dalian of ionic conductivity
Method as defined in the assembling and performance test of 2.4.5 monocells is by the present invention's in professional degree of Polytechnics master thesis
Polyacrylonitrile battery diaphragm carries out monocell assembling and tests the conductivity of diaphragm, as shown in table 2.
Table 2：Conductivity table
| Conductivity (S/cm) | |
| Embodiment 2 | 0.0034 |
| Embodiment 3 | 0.0064 |
| Embodiment 4 | 0.0081 |
| Embodiment 5 | 0.0073 |
| Embodiment 6 | 0.0092 |
| Embodiment 7 | 0.0153 |
| Embodiment 8 | 0.0109 |
Part raw material sources are as follows in embodiment：
Polybenzimidazoles：Molecular weight about 250,000, powdery, the strange prosperous plasticizing Co., Ltd in Suzhou.
Perfluorinated sulfonic acid polymer：Abbreviation Nafion, model：N836376Nafion R-1100 resins, Jining Hua Kai resin
Co., Ltd.
N-Methyl pyrrolidone：No. CAS：872-50-4.
Polyacrylonitrile：Model：P60C, molecular weight are 150,000, Shaoxing Jie Ma composite materials Co., Ltd.
Polyvinylpyrrolidone：No. CAS：9003-39-8 is provided, model by Jin Ao Chemical Co., Ltd.s of Anhui Province
PVPk30, molecular weight：40000.
DMAC N,N' dimethyl acetamide：No. CAS：127-19-5.
Montmorillonite, montmorillonite powder：3000 mesh of grain size, specific surface area 240m2/ g, mineral products processing factory of Lingshou County Hengchang.
Silica：Aerosil, also known as white carbon, grain size are 10~20nm, and the excellent rope chemical science and technology in Shandong is limited
Company.
Cetyl trimethylammonium bromide：No. CAS：57-09-0.
Embodiment 9-16
A kind of zinc-bromine flow battery, including positive plate, negative plate and be arranged between the positive plate and negative plate
Battery diaphragm.
The positive plate be graphite cake (be purchased from Zibo Ou Zheng carbons Co., Ltd, length × width x thickness for 6cm × 6cm ×
0.5cm)。
The negative plate be graphite cake (be purchased from Zibo Ou Zheng carbons Co., Ltd, length × width x thickness for 6cm × 6cm ×
0.5cm)。
Polyacrylonitrile battery diaphragm prepared by the battery diaphragm difference corresponding embodiment 2-8 of embodiment 9-15.
The battery diaphragm of embodiment 16 is polyacrylonitrile battery diaphragm prepared by comparative example 1.
The zinc-bromine flow battery further includes the general electrolyte of the industry, and embodiment 9-16 is all made of by 2.5mol/L bromines
Change the electrolyte of zinc, 2.5mol/ sodium chloride, excess water composition.
Test case 3：
Efficiency for charge-discharge is tested：By the zinc-bromine flow battery of embodiment 9-16 by Sun Yu " zinc-bromine flow battery diaphragm
The assembling of 2.4.5 monocells carries out group in 2015 professional degree of Dalian University of Technology master thesis of preparation and performance study "
Dress.Charge and discharge cycles test is carried out with 1C between 3.0~4.2V, is recycled 50 times, efficiency for charge-discharge is calculated.
Efficiency for charge-discharge refers to the ratio that the capacity that electric discharge obtains divided by the capacity that a preceding charge step provides obtain.Change speech
It, efficiency for charge-discharge, CEfficiency=Dn+1/Cn× 100%, wherein D is discharge capacity, and C is charging capacity, and n is cycle-index.It fills
Discharging efficiency is as shown in table 3.
Table 3：Efficiency for charge-discharge table
The longitudinal tensile strength of zinc-bromine flow battery prepared by the present invention, battery diaphragm is heat-shrinked in 168MPa or more
Rate is 1.2% hereinafter, having excellent mechanical performance.The zinc-bromine flow battery of the present invention, being capable of large capacity, prolonged charge and discharge
Electricity, efficiency for charge-discharge are high.Moreover, battery diaphragm of the invention is also equipped with higher conductivity.Conductivity is higher, and resistance is got over
It is small, illustrate that the obstruction ability that diaphragm flows electronics is smaller, the chemical property of diaphragm is more excellent.
Claims (3)
1. a kind of zinc-bromine flow battery, including positive plate, negative plate and the electricity being arranged between the positive plate and negative plate
Pond diaphragm, it is characterised in that：
The positive plate is metal class, such as Pb, Ti etc.；Charcoal element class, such as graphite, carbon cloth, carbon felt；Composite material class, it is such as conductive
Polymer, polymer composite etc., the positive plate are preferably one kind in graphite cake, carbon felt, graphite felt or carbon cloth；
The negative plate is metal class, such as Pb, Ti etc.；Charcoal element class, such as graphite, carbon cloth, carbon felt；Composite material class, it is such as conductive
Polymer, polymer composite etc., the negative plate are preferably one kind in graphite cake, carbon felt, graphite felt or carbon cloth；
The battery diaphragm is composite material class, such as conducting polymer, polymer composite, preferably single layer PE, PP films,
3 layers of PP, PE film, Nafion membrane or polyacrylonitrile basement membrane, the battery diaphragm are preferably polyacrylonitrile battery diaphragm.
2. zinc-bromine flow battery as described in claim 1, it is characterised in that：The polyacrylonitrile battery diaphragm uses following sides
Method is prepared：
High molecular polymer is dissolved in organic solvent by S1, obtains the solution A that high molecular polymer mass fraction is 10~15%；
Stabilizer, polyacrylonitrile, polyvinylpyrrolidone are added in n,N-dimethylacetamide by S2, obtain solution B；
S3 scratches solution B on a glass, stands, and forms film；Film is put into together with glass plate in solidification liquid and is impregnated；It tears
Lower film rinses, dry, obtains polyacrylonitrile basement membrane；
Solution A is coated on polyacrylonitrile basement membrane by S4, is dried to get the polyacrylonitrile battery diaphragm.
3. zinc-bromine flow battery as claimed in claim 2, it is characterised in that：The high molecular polymer is polybenzimidazoles
And/or perfluorinated sulfonic acid polymer.
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