CN110137506A - Bipolar plate of redox flow battery, preparation method and its material microballoon - Google Patents
Bipolar plate of redox flow battery, preparation method and its material microballoon Download PDFInfo
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- CN110137506A CN110137506A CN201810136269.0A CN201810136269A CN110137506A CN 110137506 A CN110137506 A CN 110137506A CN 201810136269 A CN201810136269 A CN 201810136269A CN 110137506 A CN110137506 A CN 110137506A
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- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000004698 Polyethylene Substances 0.000 claims description 75
- 229920000573 polyethylene Polymers 0.000 claims description 75
- 239000006229 carbon black Substances 0.000 claims description 47
- 238000000498 ball milling Methods 0.000 claims description 41
- 229920000642 polymer Polymers 0.000 claims description 32
- 238000007731 hot pressing Methods 0.000 claims description 30
- 238000000227 grinding Methods 0.000 claims description 16
- 239000004020 conductor Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 5
- 239000002861 polymer material Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 3
- 239000012744 reinforcing agent Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
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- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 239000002245 particle Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 27
- 239000000843 powder Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
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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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- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Fuel Cell (AREA)
Abstract
The invention discloses a kind of bipolar plate of redox flow battery, preparation method and its material microballoons.The present invention provides a kind of liquid stream bipolar plate material microballoon A, and bipolar plate of redox flow battery has been prepared by it, the electric conductivity and mechanical performance for the bipolar plate of redox flow battery that this method is prepared are good, and preparation process is simple, it is environmentally friendly, it is easy to industrialize.
Description
Technical field
The present invention relates to bipolar plate of redox flow battery, preparation method and its material microballoons.
Background technique
Along with renewable energy, the accelerated development of distributed micro-grid and the wisdom energy, being promoted, renewable energy is grid-connected
The energy storage technology to play a significant role in terms of rate, balance grid stability is more and more concerned.And in numerous large capacity energy storage skills
In art route, all-vanadium flow battery has been shown one's talent.
Compared with other energy storage technologies, all-vanadium flow battery energy storage technology is big, safe and reliable because of its long service life, scale
Etc. advantage outstanding, become one of the one preferred technique of scale energy storage.Bipolar plates are one of flow battery critical components, have and pass
It passs electronics and separates the effect of positive and negative anodes electrolyte, to its good electric conductivity, resistance to chemical corrosion and excellent machine
Tool performance is proposed higher requirement.Therefore, the preparation process of bipolar plates also has received widespread attention.
Such as: Chinese patent application CN101567452A discloses patent of invention, and " a kind of composite material of flow battery is double
Pole plate preparation method ", it proposes using solwution method mixing, the tape casting casting and die pressing molding, three kinds of preparations successively combined
Method, to prepare the bipolar plates of high conductivity.But the technical solution uses a large amount of organic solvents, in curtain coating casting process
Middle solvent can be evaporate into atmosphere, be unfavorable for environmental protection.
Chinese patent application CN106099121A is disclosed patent of invention " bipolar plates and its preparation method and application ", is proposed
Conductive pattern layer is coated on the two sides of the bipolar plates ontology of preparation, to achieve the purpose that the sheet resistance for reducing bipolar plates.It should
Bipolar plate surfaces, which need to apply, pours the organic solvent for being mixed with conductive material, obtains bipolar plates after volatilization drying, this process will evaporate
A large amount of organic solvents, are unfavorable for environmental protection；In addition, the bipolar plates of conductive pattern layer are unfavorable for battery assembly, it be easy to cause figure layer
Damage, influence battery performance.
Chinese patent application CN106299389A discloses patent of invention " bipolar plate of all-vanadium redox flow battery and its preparation side
Method ", proposing through thermosetting resin is matrix, and is combined by conductive network of nickel screen, nickel screen surface grafting carbon
Nanotube, prepared bipolar plates electric conductivity are stablized, and electric conductivity is good.But the technical solution uses metal mesh and thermosetting property
Resin compounded can be chronically in strong acidic environment during actual battery operation, and the nickel screen in bipolar plates is easy by strong acid
The corrosion of solution, to influence the service life of bipolar plates.
Chinese patent application CN106848346A discloses patent of invention " flow battery bipolar plates and preparation method thereof ",
It proposes bipolar plates to be combined by five-layer structure, including graphite felt/carbon felt, porous structure carbon/metal base, polyphosphazene polymer
Object material, porous structure carbon/metal base, graphite felt/carbon felt are closed, so that the bipolar plates mechanical performance and electric conductivity prepared
It can be excellent.The technical solution is combined using five-layer structure, and preparation process is extremely complex, and every layer requires thickness very thin, no
Conducive to processing, higher cost.
As it can be seen that the preparation of flow battery bipolar plates at present has that two: one are preparation process complexity or to ring
Border is unfriendly, is not suitable for industrialization；The other is the electric conductivity and mechanical performance of the bipolar plates being prepared can not get both.Example
Such as, while the electric conductivity of bipolar plates improves, while mechanical performance decline or mechanical performance improve, electric conductivity decline,
Prevent the comprehensive performance of bipolar plates is from being significantly improved.
Therefore, how to provide a kind of suitable industrialization, green and liquid stream that electric conductivity and mechanical performance can be taken into account
Cell bipolar plate is those skilled in the art's a great problem in the urgent need to address.
Summary of the invention
The technical problem to be solved by the present invention is in order to overcome liquid stream bipolar plates electric conductivity and machinery in the prior art
Performance cannot be taken into account, or even if available conductive and satisfactory mechanical property bipolar plates, but preparation process is complicated, operation is tired
Difficult, defect unfriendly to environment or at high cost, to provide a kind of liquid stream bipolar plates, preparation method and its material microballoon.
The liquid stream bipolar plates electric conductivity and mechanical performance being prepared by the liquid stream bipolar plate material microballoon are good, and prepare
Simple process, it is environmentally friendly, it is easy to industrialize.
The present invention provides a kind of bipolar plate of redox flow battery material microballoon A, the bipolar plate of redox flow battery material microballoon A's
Partial size is 5~20 μm；It includes microballoon B and high molecular polymer microballoon that mass ratio is 1:1~1:4；The microballoon B includes matter
Amount is than the high molecular polymer and conductive material for 1:1~4:1 (such as 2:1), and the conductive material is coated on the high score
Sub- polymer surfaces；The partial size of the microballoon B and the high molecular polymer microballoon is each independently 5~20 μm.
In the present invention, the bipolar plate of redox flow battery material microballoon A does not include auxiliary agent.
The auxiliary agent refers to that this field prepares auxiliary agent commonly used by bipolar plate of redox flow battery, the optional self-dispersing of auxiliary agent
One of agent, surfactant, reinforcing agent and compatilizer are a variety of.
In the present invention, the high molecular polymer in the high molecular polymer and the high molecular polymer microballoon is this
Common high molecular polymer when bipolar plate of redox flow battery is prepared in field.
The high molecular polymer can be thermoplastic polymer, can be selected from polyethylene (PE), polypropylene (PP), polyvinyl chloride
(PVC), one of polystyrene (PS) and acrylonitrile-butadiene-styrene copolymer (ABS) or a variety of；The copolymer
Number-average molecular weight be 200000-600000.
The density of the high molecular polymer can be 0.5-1.0g/cm3, such as 0.9g/cm3。
In the present invention, the conductive material is to prepare common conductive material when bipolar plate of redox flow battery in the art；Institute
Stating conductive material can be selected from one of graphite, carbon black and graphene or a variety of.
In the present invention, preferably, the microballoon B is identical with the partial size of the high molecular polymer microballoon.
In the present invention, the partial size of the microballoon B and the high molecular polymer microballoon is each independently 10 μm~25 μm,
Such as 20 μm.
In the present invention, the microballoon B can be prepared by the following method to obtain, and it includes following steps: by the mass ratio
It is prepared for the high molecular polymer and conductive material of 1:1~4:1 by ball milling.
In the present invention, the high molecular polymer microballoon can be by the way that the high molecular polymer to be prepared by ball milling
It arrives.
In the ball milling preparation process of the microballoon B and the high molecular polymer microballoon:
The ratio of grinding media to material when ball milling can be 1:1-5:1, such as 2:1.
Whether time when the ball milling can be according to achieving the effect that crush and be uniformly mixed and judges (such as the ball milling
Time can be 20min-60min, then such as 30min.
The revolving speed when ball milling can be 200-700r/min, such as 500r/min.
The present invention also provides the preparation methods of bipolar plate of redox flow battery material microballoon A a kind of, and it includes following steps
Suddenly, microballoon is prepared in the microballoon B and high molecular polymer microballoon stirring.
The stirring can be used high-speed mixer, and revolving speed can be 500r/min, for example, stirred in high-speed mixer when
Between be 20min.
The present invention also provides a kind of preparation methods of bipolar plate of redox flow battery, and it includes following steps: will on substrate
The bipolar plate of redox flow battery material microballoon A passes through hot pressing.
In the present invention, the preparation method can carry out under organic solvent-free.
In the present invention, the hot pressing can refer to the instrument and parameter of hot pressing when preparing bipolar plate of redox flow battery in the art,
Such as the hot pressing instrument uses vulcanizing press.
Wherein, the hot pressing temperature can be 170-230 DEG C, such as 190~200 DEG C.
Wherein, the hot pressing pressure can be 2-15MPa, for example, 10MPa.
Wherein, the hot pressing time can be 2-20min, for example, 3min.
The present invention provides a kind of bipolar plate of redox flow batteries prepared by the above method.
The thickness of the bipolar plate of redox flow battery can be 0.5-5mm (such as 0.5-3.0mm, then such as 1mm), resistivity
It can be 1-100 Ω .cm (such as 16~40 Ω .cm) that mechanical properties tensile strength can be 10-50MPa (such as 17~22MPa),
Elongation at break can be 7%~14%.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can any combination to get the present invention it is each preferably
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
(1) bipolar plate of redox flow battery electricity and mechanical performance provided by the present invention are good；
(2) bipolar plate of redox flow battery provided by the present invention can be prepared under organic solvent-free effect, to environment friend
It is good；
(3) bipolar plate of redox flow battery provided by the present invention is assembled in 5KW all-vanadium flow battery pile, in 40mA/cm2
Current density under current efficiency reach 84% or more, voltage efficiency is that can reach 76% or more, and energy efficiency can reach
64% or more.
(4) this method by macromolecule polymer material is not added during mixing with conductive material it is any for example
The auxiliary agents such as reinforcing agent.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of bipolar plate of redox flow battery in embodiment 1.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
In following embodiment:
PE is purchased from Qatar's petrochemical industry；
HDPE high density polyethylene (HDPE) is the 5000S of Daqing petrochemical；
PP is the T30S of Zhenghai refinery；
Carbon black is the EC-300J of section's qin；
Ball mill is following PM-0.2A of wound；
High-speed mixer is the 10L batch mixer of Laizhou Ze Lin chemical；
Vulcanizer is the XLB-1 that Yuyao City must found hydraulic mechanical & electrical equipment factory；
Embodiment 1
1, by the mixture of polyethylene (PE) particle and carbon black, with mass ratio, for 2:1, (wherein, the quality of PE is 200g, charcoal
Black quality is 100g, and the density of PE is 0.5g/cm3) ratio be added to ball milling in ball mill, the density of PE particle is
0.9g/cm3, the specific surface area of carbon black is 200m2/ g, ratio of grinding media to material 2:1, Ball-milling Time 30min, revolving speed 500r/min, system
The mixture of standby PE and carbon black, prepared microballoon (i.e. microballoon B) partial size are 5 microns.
2, PE particle is added to ball milling in ball mill, the density of PE particle is 0.9g/cm3, ratio of grinding media to material 2:1, ball milling
Time is 30min, revolving speed 500r/min, prepares PE powder, and prepared microspherulite diameter is 5 microns.
3, by PE and the mixture of carbon black that mass ratio is 1:1, PE powder in high-speed mixer, revolving speed 500r/min,
Middle stirring 20min, obtains PE- black stock, and prepared microballoon (i.e. microballoon A) partial size is 10 microns.
4, PE- black stock (microballoon A) is put into hot pressing in vulcanizing press, hot pressing temperature is 190 DEG C, pressure
10MPa, time 3min obtain conductive bipolar plates, with a thickness of 1mm.
Embodiment 2
1, by the mixture of PE particle and carbon black, with mass ratio, for 2:1, (wherein, the quality of PE is 200g, the quality of carbon black
For 100g, the density of PE is 1.0g/cm3) ratio be added to ball milling in ball mill, the density of PE particle is 0.9g/cm3, carbon black
Specific surface area be 200m2/ g, ratio of grinding media to material 2:1, Ball-milling Time 30min, revolving speed 500r/min prepare PE and carbon black
Mixture, prepared microspherulite diameter are 10 microns.
2, PE particle is added to ball milling in ball mill, the density of PE particle is 0.9g/cm3, ratio of grinding media to material 3:1, ball milling
Time is 30min, revolving speed 500r/min, prepares PE powder, and prepared microspherulite diameter is 10 microns.
3, mixture, the PE powder of PE and carbon black that mass ratio is 1:1 are stirred into 20min, revolving speed in high-speed mixer
For 500r/min, PE- black stock is obtained, prepared microspherulite diameter is 10 microns.
4, PE- black stock is put into hot pressing in vulcanizing press, hot pressing temperature is 200 DEG C, pressure 10MPa, the time
3min obtains conductive bipolar plates, with a thickness of 1mm.
Embodiment 3
1, by the mixture of PE particle and carbon black, with mass ratio, for the ratio of 2:1, (wherein, the quality of PE is 200g, carbon black
Quality be 100g, the density of PE is 0.9g/cm3) it is added to ball milling in ball mill, the density of PE particle is 0.9g/cm3, carbon black
Specific surface area be 200m2/ g, ratio of grinding media to material 2:1, Ball-milling Time 30min, revolving speed 500r/min prepare PE and carbon black
Mixture, prepared microspherulite diameter are 10 microns.
2, PE particle is added to ball milling in ball mill, the density of PE particle is 0.9g/cm3, ratio of grinding media to material 2:1, ball milling
Time is 15min, revolving speed 500r/min, prepares PE powder, and prepared microspherulite diameter is 25 microns.
3, mixture, the PE powder of PE and carbon black that mass ratio is 1:1 are stirred into 20min, revolving speed in high-speed mixer
For 500r/min, PE- black stock is obtained, prepared microspherulite diameter, which is 10-25 microns, to be differed.
4, PE- black stock is put into hot pressing in vulcanizing press, hot pressing temperature is 200 DEG C, pressure 10MPa, the time
3min obtains conductive bipolar plates, with a thickness of 1mm.
Embodiment 4
1, by the mixture of PE particle and carbon black, with mass ratio, for 2:1, (wherein, the quality of PE is 200g, the quality of carbon black
For 100g, the density of PE is 0.9g/cm3) ratio be added to ball milling in ball mill, the density of PE particle is 0.9g/cm3, carbon black
Specific surface area be 200m2/ g, ratio of grinding media to material 2:1, Ball-milling Time 30min, revolving speed 500r/min prepare PE and carbon black
Mixture, prepared microspherulite diameter are 10 microns.
2, PP particle is added to ball milling in ball mill, the density of PP particle is 0.9g/cm3, ratio of grinding media to material 2:1, ball milling
Time is 30min, revolving speed 500r/min, prepares PP powder, and prepared microspherulite diameter is 10 microns.
3, mixture, the PP powder of PE and carbon black that mass ratio is 1:1 are stirred into 20min, revolving speed in high-speed mixer
For 500r/min, PE-PP- black stock is obtained, prepared microspherulite diameter is 10 microns.
4, PE-PP- black stock being put into hot pressing in vulcanizing press, hot pressing temperature is 200 DEG C, pressure 10MPa, when
Between 3min, conductive bipolar plates are obtained, with a thickness of 1mm.
Embodiment 5
1, by the mixture of PE particle and carbon black, with mass ratio, for 1:1, (wherein, the quality of PE is 100g, the quality of carbon black
For 100g, the density of PE is 0.9g/cm3) ratio be added to ball milling in ball mill, the density of PE particle is 0.9g/cm3, carbon black
Specific surface area be 200m2/ g, ratio of grinding media to material 2:1, Ball-milling Time 30min, revolving speed 500r/min prepare PE and carbon black
Mixture, prepared microspherulite diameter are 20 microns.
2, PE particle is added to ball milling in ball mill, the density of PE particle is 0.9g/cm3, ratio of grinding media to material 2:1, ball milling
Time is 30min, revolving speed 500r/min, prepares PE powder, and prepared microspherulite diameter is 20 microns.
3, mixture, the PE powder of PE and carbon black that mass ratio is 1:4 are stirred into 20min, revolving speed in high-speed mixer
For 500r/min, PE- black stock is obtained, prepared microspherulite diameter is 20 microns.
4, PE- black stock is put into hot pressing in vulcanizing press, hot pressing temperature is 200 DEG C, pressure 10MPa, the time
3min obtains conductive bipolar plates, with a thickness of 1mm.
Embodiment 6
1, by the mixture of PE particle and carbon black, with mass ratio, for 4:1, (wherein, the quality of PE is 400g, the quality of carbon black
For 100g, the density of PE is 0.9g/cm3) ratio be added to ball milling in ball mill, the density of PE particle is 0.9g/cm3, carbon black
Specific surface area be 200m2/ g, ratio of grinding media to material 3:1, Ball-milling Time 30min, revolving speed 500r/min prepare PE and carbon black
Mixture, prepared microspherulite diameter are 10 microns.
2, PE particle is added to ball milling in ball mill, the density of PE particle is 0.9g/cm3, ratio of grinding media to material 2:1, ball milling
Time is 30min, revolving speed 500r/min, prepares PE powder, and prepared microspherulite diameter is 10 microns.
3, mixture, the PE powder of PE and carbon black that mass ratio is 1:1 are stirred into high-speed mixer 20min, obtained
PE- black stock, prepared microspherulite diameter are 10 microns.
4, PE- black stock is put into hot pressing in vulcanizing press, hot pressing temperature is 200 DEG C, pressure 10MPa, the time
3min obtains conductive bipolar plates, with a thickness of 1mm.
Comparative example 1
1, the mixture of PE particle and carbon black is subjected to mixed at high speed, revolving speed 500r/ with mass ratio for the ratio of 2:1
The density of min, PE particle is 0.9g/cm3, the specific surface area of carbon black is 200m2/ g prepares the mixture of PE and carbon black, prepared
Powder diameter be 20-50 microns.
2, PE- black stock is put into hot pressing in vulcanizing press, hot pressing temperature is 190 DEG C, pressure 10MPa, the time
3min obtains conductive bipolar plates.
Comparative example 2
1, by the mixture of PE particle and carbon black, with mass ratio, for 2:1, (wherein, the quality of PE is 200g, the quality of carbon black
For 100g, the density of PE is 0.9g/cm3) ratio be added to ball milling in ball mill, the density of PE particle is 0.9g/cm3, carbon black
Specific surface area be 200m2/ g, ratio of grinding media to material 2:1, Ball-milling Time 30min, revolving speed 500r/min prepare PE and carbon black
Mixture, prepared microspherulite diameter are 10 microns.
2, the mixture after PE- carbon black mixed at high speed is put into hot pressing in vulcanizing press, hot pressing temperature is 190 DEG C, pressure
Power 10MPa, time 3min obtain conductive bipolar plates.
Comparative example 3
1, by the mixture of PE particle and carbon black, with mass ratio, for 2:1, (wherein, the quality of PE is 200g, the quality of carbon black
For 100g, the density of PE is 0.9g/cm3) ratio be added to ball milling in ball mill, the density of PE particle is 0.9g/cm3, carbon black
Specific surface area be 200m2/ g, ratio of grinding media to material 2:1, Ball-milling Time 30min, revolving speed 500r/min prepare PE and carbon black
Mixture, prepared microspherulite diameter are 10 microns.
2, the mixture of PE and carbon black is stirred into 20min in high-speed mixer 500r/min, obtains the mixing of PE- carbon black
Object, prepared microspherulite diameter are 10 microns.
3, the mixture after PE- carbon black mixed at high speed is put into hot pressing in vulcanizing press, hot pressing temperature is 190 DEG C, pressure
Power 10MPa, time 3min obtain conductive bipolar plates.
Effect example 1
The electric conductivity and mechanical performance for the bipolar plates that above-described embodiment 1~6 and comparative example 1~3 are prepared
It is tested.
| Number | Resistance (Ω) | Tensile strength (20Mpa) | Elongation at break |
| Embodiment 1 | 28 | 20 | 10% |
| Embodiment 2 | 23 | 22 | 11% |
| Embodiment 3 | 20 | 18 | 8.50% |
| Embodiment 4 | 19 | 17 | 8% |
| Embodiment 5 | 16 | 19 | 7% |
| Embodiment 6 | 40 | 25 | 14% |
| Comparative example 1 | 120 | 22 | 15% |
| Comparative example 2 | 108 | 15 | 7.8% |
| Comparative example 3 | 38 | 14 | 7.5% |
Effect example 2
The bipolar plates that above-described embodiment 1~6 and comparative example 1~3 are prepared are assembled to 5KW all-vanadium flow battery
In pile, in 40mA/cm2Current density under test its current efficiency, voltage efficiency, energy efficiency and electrolyte utilization rate.
Current efficiency, voltage efficiency, energy efficiency are all made of the electro-chemical test of new Weir Electronics Co., Ltd., Shenzhen
Instrument 5V6A is tested, as a result as shown in the table.
| Current efficiency | Voltage efficiency | Energy efficiency | |
| Embodiment 1 | 90% | 80% | 72% |
| Embodiment 2 | 91% | 83% | 76% |
| Embodiment 3 | 88% | 78% | 69% |
| Embodiment 4 | 87% | 78% | 68% |
| Embodiment 5 | 85% | 76% | 65% |
| Embodiment 6 | 84% | 76% | 64% |
| Comparative example 1 | 78% | 75% | 59% |
| Comparative example 2 | 80% | 76% | 61% |
| Comparative example 3 | 82% | 74% | 61% |
Claims (10)
1. a kind of bipolar plate of redox flow battery material microballoon A, which is characterized in that the grain of the bipolar plate of redox flow battery material microballoon A
Diameter is 5~20 μm；It includes microballoon B and high molecular polymer microballoon that mass ratio is 1:1~1:4；The microballoon B includes quality
Than the high molecular polymer and conductive material for 1:1~4:1, and the conductive material is coated on the high molecular polymer table
Face；The partial size of the microballoon B and the high molecular polymer microballoon is each independently 5~20 μm.
2. bipolar plate of redox flow battery material microballoon A as described in claim 1, which is characterized in that the bipolar plate of redox flow battery
Material microballoon A does not include auxiliary agent, and the auxiliary agent is for example selected from one of dispersing agent, surfactant, reinforcing agent and compatilizer
Or it is a variety of；
And/or the high molecular polymer is thermoplastic polymer, such as selected from polyethylene, polypropylene, polyvinyl chloride, polyphenyl
One of ethylene and acrylonitrile-butadiene-styrene copolymer are a variety of；The number-average molecular weight of the copolymer is
200000-600000；
And/or the conductive material is selected from one of graphite, carbon black and graphene or a variety of.
3. bipolar plate of redox flow battery material microballoon A as described in claim 1, which is characterized in that the microballoon B and the high score
The partial size of sub- polymer microballoon is identical；
And/or the partial size of the microballoon B and the high molecular polymer microballoon is each independently 10 μm~25 μm, such as 20 μ
m；
And/or the microballoon B includes the high molecular polymer and conductive material that mass ratio is 2:1；
And/or the density of the high molecular polymer is 0.5-1.0g/cm3, such as 0.9g/cm3。
4. bipolar plate of redox flow battery material microballoon A as described in claim 1, which is characterized in that the microballoon B passes through with lower section
Method is prepared, and it includes following steps: the high molecular polymer and the conductive material for being 1:1~4:1 by mass ratio
It is prepared by ball milling；
And/or high molecular polymer microballoon described in the high score is by the way that the high molecular polymer ball milling to be prepared.
5. bipolar plate of redox flow battery material microballoon A as claimed in claim 4, which is characterized in that the microballoon B and the high score
In the ball milling preparation process of sub- polymer microballoon:
The ratio of grinding media to material when ball milling is 1:1-5:1, such as 2:1；
And/or the time when ball milling is 20min-60min, such as 30min；
And/or the revolving speed when ball milling is 200-700r/min, such as 500r/min.
6. a kind of preparation method of the bipolar plate of redox flow battery material microballoon A as described in any one of Claims 1 to 5, packet
Containing following steps, microballoon is prepared in the microballoon B and high molecular polymer microballoon stirring.
7. the preparation method of bipolar plate of redox flow battery material microballoon A as claimed in claim 6, which is characterized in that the stirring
Shi Caiyong high-speed mixer, the mixing time of the high-speed mixer are 20min.
8. a kind of preparation method of bipolar plate of redox flow battery, which is characterized in that comprise the steps of: the liquid stream on substrate
Cell Bipolar plate material microballoon A passes through hot pressing.
9. bipolar plate of redox flow battery as claimed in claim 8, which is characterized in that the preparation method under organic solvent-free into
Row；
And/or vulcanizing press is used when the hot pressing；
And/or the hot pressing temperature is 170-230 DEG C, such as 190~200 DEG C；
And/or the hot pressing pressure is 2-15MPa, for example, 10Mpa；
And/or the hot pressing time is 2-20min, for example, 3min.
10. a kind of bipolar plate of redox flow battery that preparation method as claimed in claim 8 or 9 is prepared.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1776944A (en) * | 2005-09-27 | 2006-05-24 | 武汉理工大学 | Method for improving conductivity of bipolar plate of high-conducting composite material |
| CN101308924A (en) * | 2007-05-18 | 2008-11-19 | 中国科学院大连化学物理研究所 | Flexibility enhanced bipolar plate for liquid energy-storing battery and manufacture thereof |
| CN101567452A (en) * | 2009-04-20 | 2009-10-28 | 清华大学 | Preparation method of liquid flow battery composite material bipolar plate |
| CN104332641A (en) * | 2014-08-28 | 2015-02-04 | 清华大学 | Preparation method of composite bipolar plate |
| US20150364768A1 (en) * | 2010-04-16 | 2015-12-17 | Sumitomo Electric Industries, Ltd. | Redox flow battery cell stack |
-
2018
- 2018-02-09 CN CN201810136269.0A patent/CN110137506B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1776944A (en) * | 2005-09-27 | 2006-05-24 | 武汉理工大学 | Method for improving conductivity of bipolar plate of high-conducting composite material |
| CN101308924A (en) * | 2007-05-18 | 2008-11-19 | 中国科学院大连化学物理研究所 | Flexibility enhanced bipolar plate for liquid energy-storing battery and manufacture thereof |
| CN101567452A (en) * | 2009-04-20 | 2009-10-28 | 清华大学 | Preparation method of liquid flow battery composite material bipolar plate |
| US20150364768A1 (en) * | 2010-04-16 | 2015-12-17 | Sumitomo Electric Industries, Ltd. | Redox flow battery cell stack |
| CN104332641A (en) * | 2014-08-28 | 2015-02-04 | 清华大学 | Preparation method of composite bipolar plate |
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