CN109524682A - A kind of metal compound bipolar plate used for all-vanadium redox flow battery and preparation method thereof - Google Patents
A kind of metal compound bipolar plate used for all-vanadium redox flow battery and preparation method thereof Download PDFInfo
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- CN109524682A CN109524682A CN201811342099.8A CN201811342099A CN109524682A CN 109524682 A CN109524682 A CN 109524682A CN 201811342099 A CN201811342099 A CN 201811342099A CN 109524682 A CN109524682 A CN 109524682A
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
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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
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Abstract
The present invention relates to bipolar plates preparation field, especially a kind of metal compound bipolar plate used for all-vanadium redox flow battery and preparation method thereof.Metal compound bipolar plate is made of metal master structure and surface anticorrosion functional layer, and metal master structure assigns the good electric conductivity of bipolar plates, air-tightness and mechanicalness, and surface anticorrosion functional layer assigns the good corrosion resistance of bipolar plates and interfacial contact.Above-mentioned metal master structure and surface anticorrosion functional layer are suppressed by thermal spraying, cold spraying, high temperature and the techniques such as coating are combined into organic whole.This metal compound bipolar plate shows high electron conduction, while having both good intensity, corrosion resistance and processability, and preparation process is compared with simple, cost of material is low, it is easy to accomplish large-scale production.
Description
Technical field
The present invention relates to bipolar plates preparation field, especially a kind of metal compound bipolar plate used for all-vanadium redox flow battery and its system
Preparation Method.
Background technique
Whole vanadium oxide reduction all-vanadium flow battery be it is a kind of environmental protection and large capacity can depth charge and discharge energy-storage battery.The electricity
Pond acts not only as the mating energy storage device of electricity generation system of the renewable energy such as solar energy, wind energy, and is also used as electricity
The peak adjusting device of net improves transmission of electricity quality, ensures power grid security, obtain in states such as Japan, the U.S., Canada and Australia
Demonstrating running.
Bipolar plates are also referred to as collector plate, are one of the critical materials of all-vanadium flow battery heap.It is mainly collected current, divides
Oxygen barrier agent and reducing agent, and by reactant evenly distribute electrode everywhere.In order to improve the energy density of pile, all-vanadium flow
Battery pack is generally assembled by filter press mode, and bipolar plates used must have following performance: (1) realize connection electric between single pond,
It must be made of the material of well conducting；(2) electrode active material is by the public duct that is made of bipolar plates, sealing element etc.,
Inlet tube through each single pond imports each single pond, and is assigned to electrode everywhere by even flow field；(3) due to positive and negative electrode activity
Material is different, it is desirable that bipolar plates have high barrier property, i.e., must be non-porous；(4) it under all-vanadium flow battery environment, constitutes bipolar
The material of plate must be corrosion-resistant, to realize the lifetime goal of battery pack, generally 8~15 years；(5) bipolar plates must be the good of heat
Conductor；(6) in order to facilitate large-scale promotion, the cost of material and preparation cost of bipolar plates must be very low.
Currently, researcher develops conductive plastic bi-polar plate, graphite bi-polar plate and metal double polar plates.Conductive plastic bi-polar plate
There are irreconcilable contradictions between electric conductivity and mechanical strength, it is difficult to obtain the bipolar plates of excellent combination property；Graphite bi-polar plate
Production technology it is relatively very complicated, cause its preparation cost higher, be difficult to promote in extensive energy-storage pile field；Metal is double
Pole plate has the advantages such as good electric conductivity, air-tightness, mechanicalness and processability, but chemical corrosion resistance difference is to limit it extensively
The bottleneck problem of general application.
Summary of the invention
The purpose of the present invention is to provide a kind of metal compound bipolar plates used for all-vanadium redox flow battery and preparation method thereof.This pair
The metal master structure of pole plate assigns the good electric conductivity of bipolar plates, air-tightness and mechanicalness, and surface anticorrosion functional layer assigns double
The good corrosion resistance of pole plate and interfacial contact.Mainly pass through the techniques guarantee fund owners such as thermal spraying, cold spraying or high temperature compacting
Body structure and anti-corrosion function layer are combined into organic whole.This composite dual-electrode plates has high electron conduction, while having both good
Good intensity, corrosion resistance and processability.
The technical scheme is that
A kind of metal compound bipolar plate used for all-vanadium redox flow battery, composite dual-electrode plates mainly include high-conductivity metal plate and
One layer of anti-corrosion function layer of cladding process preparation is utilized in metal sheet surface, in which:
High-conductivity metal plate is the excellence conductor of electronics, and constituent material is stainless steel plate, titanium plate, zine plate, aluminium alloy plate
Or titanium alloy sheet, metal plate with a thickness of 0.2mm~5mm；
Anti-corrosion function layer is compact texture, conductive, while having the characteristic of barrier gas, fluid molecule, is constituted
Material is stainless steel powder, titanium valve, nickel powder, graphene, carbon nanotube, polypyrrole, polyphenylene sulfide, polyaniline or polythiophene, function
Layer is with a thickness of 50 μm~2000 μm.
The metal compound bipolar plate used for all-vanadium redox flow battery, cladding process are that a kind of material can be made in metal plate table
The technique of face excellent bonds, the technique are thermal spraying, cold spraying, hot pressing, magnetron sputtering or coating.
The bonding pattern of the metal compound bipolar plate used for all-vanadium redox flow battery, metal plate and anti-corrosion function interlayer is to change
Learn bonding, physical absorption or the mixing of two ways.
The metal compound bipolar plate used for all-vanadium redox flow battery, anti-corrosion function layer avoids composite dual-electrode plates from being corroded, double
The corrosion that pole plate faces is that can reduce the destruction of bipolar plates performance, especially electric conductivity and air-tightness, and main includes changing
Learn burn into electrochemical corrosion or biological corrosion.
The metal compound bipolar plate used for all-vanadium redox flow battery, metal plate play electric conductivity, air-tightness and mechanicalness, machine
Tool is the tension mechanical strength and bending resistance mechanical strength of bipolar plates, and wherein tension mechanical strength is greater than 50MPa, and bending resistance is mechanical strong
Degree is greater than 30MPa.
The preparation method of the metal compound bipolar plate used for all-vanadium redox flow battery, this method include at metal sheet surface
Reason, composite anti-corrosive functional layer and post-processing step, the final composite dual-electrode plates for obtaining excellent combination property.
The preparation method of the metal compound bipolar plate used for all-vanadium redox flow battery, metal sheet surface processing are metal plate
Surface cleaning processing and roughening treatment, to increase the binding force of remaining anti-corrosion function layer.
The preparation method of the metal compound bipolar plate used for all-vanadium redox flow battery post-processes to adjust the surface of bipolar plates
Roughness mainly guarantees that its surface is smooth, smooth by mechanical means, in favor of cell sealing.
The preparation method of the metal compound bipolar plate used for all-vanadium redox flow battery, composite dual-electrode plates integral thickness are
0.25mm~5.5mm.
Design philosophy of the invention is:
Metal double polar plates are that substitution manufacturing cost is high, electric conductivity is bad, poor reliability graphite bi-polar plate, conductive plastics are double
The preferable selection of pole plate, but the urgent needs such as forming accuracy, Anticorrosion solve.The present invention is set by optimizing the micro-nano structure of bipolar plates
Meter, the collocation of different materials and preparation process etc., drawing up standby a kind of has both the new of metal double polar plates and graphite bi-polar plate
Type composite dual-electrode plates used for all-vanadium redox flow battery, and then promote the technological development of high-performance all-vanadium flow battery heap.
The advantages of the present invention are:
1, the present invention is based on metal materials to have fabulous electric conductivity, and resistance toization of metal plate is improved using anti-corrosion function layer
, graphene and carbon fiber constructions novel conductive network, realize the bipolar plate design and preparation of excellent combination property, the bipolar plates
Have both good electric conductivity, air-tightness, mechanicalness, corrosion resistance and economy.
2, the present invention constructs the composite material with specific function using sheet layer material and fibrous material jointly and may be implemented
The mutual supplement with each other's advantages of material structure and performance is an original creativity technology, can be generalized to setting for other types functional material
Meter and preparation.
3, metal compound bipolar plate of the present invention shows high electron conduction, while having both good intensity, anti-corrosion
Property and processability, and preparation process is compared with simple, cost of material is low, it is easy to accomplish large-scale production.
Specific embodiment
In the specific implementation process, metal compound bipolar plate of the present invention is by metal master structure and surface anticorrosion functional layer group
At.Metal master structure mainly include metal plate or alloy sheets (such as: stainless steel plate, titanium plate, zine plate, aluminium alloy plate and titanium alloy
Plate etc.), assign the good electric conductivity of bipolar plates, air-tightness and mechanicalness.The constituent material of surface anticorrosion functional layer is mainly gold
Belong to material or non-metallic conducting material (such as: stainless steel powder, titanium valve, nickel powder, graphene, carbon nanotube, polypyrrole, polyphenylene sulfide,
Polyaniline, polythiophene etc.), the good corrosion resistance of bipolar plates and interfacial contact are assigned, composite dual-electrode plates is avoided to be corroded, is extended
The bipolar plates service life.Above-mentioned metal master structure and surface anticorrosion functional layer pass through thermal spraying, cold spraying, high temperature compacting and coating etc.
Technique is combined into organic whole.
In the present invention, unless specified otherwise, the percentage being related to is mass percent.
In the following, being further elaborated on by embodiment to the present invention.
Embodiment 1
It in the present embodiment, chooses with a thickness of 0.8mm, 304 stainless steel plates having a size of 10cm × 10cm are leading for bipolar plates
Electric metal plate.First successively using the hydrochloric acid solution of concentration 5wt%, the aqueous acetone solution of concentration 30wt% and deionized water cleaning
Metal plate, then using 1000# sand paper polishing metal plate, until surface-brightening.
Anti-corrosion function layer is prepared using cold spray process, functional layer material is the commercial titanium that particle size range is 20 μm~40 μm
Powder.The actual conditions of cold spray process are as follows: spray gas use nitrogen, 300~400 DEG C of carrier gas temperature, powder feeding pressure 2.0~
3.0MPa, spray distance 30mm, each side spray time 2min of metal plate obtain the anti-corrosion function layer with a thickness of 200 μm.Most
Afterwards, using 2000# sand paper polishing composite dual-electrode plates.
Performance evaluation is carried out to metal compound bipolar plate.
Thickness: 1.2mm；
Tensile strength: about 120MPa；
Bending strength: about 115MPa；
Electronic conductivity: about 106S/cm.
Corrosion resistance: 80 DEG C, handle 120h in 2.5mol/L sulfuric acid solution, mass loss is less than 2%.
Embodiment 2
In the present embodiment, choose with a thickness of 0.3mm, the conductive gold that the commercial titanium plate having a size of 10cm × 10cm is bipolar plates
Belong to plate.First successively using the hydrochloric acid solution of concentration 15wt%, the aqueous acetone solution of concentration 20wt% and deionized water cleaning gold
Belong to plate, then using 1200# sand paper polishing metal plate, until surface-brightening.
Anti-corrosion function layer is prepared using hot-spraying technique (plasma spray), functional layer material be particle size range be 10 μm~
20 μm of nickel powder.Using gaseous mixture powder feeding technique, pressure value is mainly P (O2)=0.65MPa, P (C2H2)=0.35MPa, dusts
Distance 205mm.Plasma spray major parameter are as follows: gas flow of ions 10L/min, powder feeding air-flow 4L/min, surfacing distance 15mm turn
Arc current 150A is moved, arc voltage 36V, each side spray time 3min of metal plate are shifted, obtains the anti-corrosion function with a thickness of 200 μm
Ergosphere.Finally, using 1800# sand paper polishing composite dual-electrode plates.
Performance evaluation is carried out to metal compound bipolar plate.
Thickness: 0.7mm；
Tensile strength: about 132MPa；
Bending strength: about 125MPa；
Electronic conductivity: about 148S/cm.
Corrosion resistance: 60 DEG C, handle 120h in 2.5mol/L sulfuric acid solution, mass loss is less than 2%.
Embodiment 3
In the present embodiment, choose with a thickness of 2.2mm, the conductive gold that the commercial aluminium sheet having a size of 10cm × 10cm is bipolar plates
Belong to plate.First successively using the hydrochloric acid solution of concentration 30wt%, the aqueous acetone solution of concentration 50wt% and deionized water cleaning gold
Belong to plate, then using 1500# sand paper polishing metal plate, until surface-brightening.
Anti-corrosion function layer is prepared using heat pressing process, functional layer material is that the graphene that particle size range is 5nm~25nm is received
Rice piece.Heat pressing process actual conditions are as follows: the graphene nanometer sheet thin layer that a layer thickness is 2.4mm is coated in metal sheet surface, it will
Metal plate is transferred to that temperature is 240 DEG C, pressure is in the press of 55MPa together with graphene layer, and gold is completed in heat preservation, pressure maintaining 20min
Belong to plate side to prepare with a thickness of 150 μm of functional layer, the function that the metal plate other side is prepared using same method with a thickness of 150 μm
Layer.Finally, using 3000# sand paper polishing composite dual-electrode plates.
Performance evaluation is carried out to metal compound bipolar plate.
Thickness: 2.5mm；
Tensile strength: about 84MPa；
Bending strength: about 75MPa；
Electronic conductivity: about 168S/cm.
Corrosion resistance: 60 DEG C, handle 120h in 2.5mol/L sulfuric acid solution, mass loss is less than 1%.
Embodiment 4
It in the present embodiment, chooses with a thickness of 3.6mm, the commercial aluminum alloys plate having a size of 10cm × 10cm is leading for bipolar plates
Electric metal plate.It is successively clear using the hydrochloric acid solution of concentration 20wt%, the aqueous acetone solution of concentration 50wt% and deionized water first
Metal plate is washed, then using 1800# sand paper polishing metal plate, until surface-brightening.
Anti-corrosion function layer is prepared using coating processes, functional layer material is fusible conductive polyaniline aqueous solution, and quality is dense
Degree is 20%.Coating processes actual conditions are as follows: by the metal plate mass-impregnation of surface cleaning in above-mentioned polyaniline aqueous solution,
15min is kept under ultrasonic wave added, then takes out impregnating metal plate, is lain in a horizontal plane in dry in 180 DEG C of temperature of vacuum oven
4h, the last each side of metal plate obtain surface covering with a thickness of the composition metal bipolar plates of 0.2mm.
Performance evaluation is carried out to metal compound bipolar plate.
Thickness: 4.0mm；
Tensile strength: about 148MPa；
Bending strength: about 135MPa；
Electronic conductivity: about 92S/cm.
Corrosion resistance: 60 DEG C, handle 120h in 2.5mol/L sulfuric acid solution, mass loss is less than 2%.
Embodiment the result shows that, the metal compound bipolar plate that the present invention designs show good electric conductivity, corrosion resistance and
Mechanical strength.The good electric conductivity of metal plate is maintained in composite dual-electrode plates, anti-corrosion function layer play fabulous chemically-resistant,
Electrochemical corrosion.Meanwhile metal compound bipolar plate preparation process used for all-vanadium redox flow battery proposed by the present invention is simple, equipment is thrown
It provides that small, cost of material is low, large-scale production can be fast implemented.
Claims (9)
1. a kind of metal compound bipolar plate used for all-vanadium redox flow battery, which is characterized in that composite dual-electrode plates mainly include high conductivity
Metal plate and one layer of anti-corrosion function layer for utilizing cladding process to prepare in metal sheet surface, in which:
High-conductivity metal plate is the excellence conductor of electronics, and constituent material is stainless steel plate, titanium plate, zine plate, aluminium alloy plate or titanium
Alloy sheets, metal plate with a thickness of 0.2mm~5mm；
Anti-corrosion function layer is compact texture, conductive, while having the characteristic of barrier gas, fluid molecule, constituent material
For stainless steel powder, titanium valve, nickel powder, graphene, carbon nanotube, polypyrrole, polyphenylene sulfide, polyaniline or polythiophene, function thickness
Degree is 50 μm~2000 μm.
2. metal compound bipolar plate used for all-vanadium redox flow battery according to claim 1, which is characterized in that cladding process is energy
Enough make a kind of material in the technique of metal sheet surface excellent bonds, the technique be thermal spraying, cold spraying, hot pressing, magnetron sputtering or
Coating.
3. metal compound bipolar plate used for all-vanadium redox flow battery according to claim 1, which is characterized in that metal plate and anti-corrosion
The bonding pattern of function interlayer is chemical bonding, physical absorption or the mixing of two ways.
4. metal compound bipolar plate used for all-vanadium redox flow battery according to claim 1, which is characterized in that anti-corrosion function layer is kept away
Exempt from composite dual-electrode plates to be corroded, the corrosion that bipolar plates face is that can reduce bipolar plates performance, especially electric conductivity and air-tightness
Destruction, mainly include chemical attack, electrochemical corrosion or biological corrosion.
5. metal compound bipolar plate used for all-vanadium redox flow battery according to claim 1, which is characterized in that metal plate performance is led
Electrically, air-tightness and mechanicalness, mechanicalness are the tension mechanical strength and bending resistance mechanical strength of bipolar plates, and wherein tension is mechanical strong
Degree is greater than 50MPa, and bending resistance mechanical strength is greater than 30MPa.
6. the preparation method of metal compound bipolar plate used for all-vanadium redox flow battery described in a kind of one of Claims 1 to 5, feature
It is, this method includes metal sheet surface processing, composite anti-corrosive functional layer and post-processing step, finally obtains excellent combination property
Composite dual-electrode plates.
7. the preparation method of metal compound bipolar plate used for all-vanadium redox flow battery according to claim 6, which is characterized in that gold
Belong to the surface cleaning processing and roughening treatment that plate surface processing is metal plate, to increase the binding force of remaining anti-corrosion function layer.
8. the preparation method of metal compound bipolar plate used for all-vanadium redox flow battery according to claim 6, which is characterized in that after
Processing is the surface roughness of adjustment bipolar plates, mainly guarantees that its surface is smooth, smooth by mechanical means, so that battery is close
Envelope.
9. the preparation method of metal compound bipolar plate used for all-vanadium redox flow battery according to claim 6, which is characterized in that multiple
Conjunction bipolar plates integral thickness is 0.25mm~5.5mm.
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| CN201811342099.8A CN109524682A (en) | 2018-11-12 | 2018-11-12 | A kind of metal compound bipolar plate used for all-vanadium redox flow battery and preparation method thereof |
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| CN201811342099.8A CN109524682A (en) | 2018-11-12 | 2018-11-12 | A kind of metal compound bipolar plate used for all-vanadium redox flow battery and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114122422A (en) * | 2021-09-30 | 2022-03-01 | 哈尔滨工业大学（威海） | Preparation method of surface microstructure of bipolar plate of fuel cell |
| CN116396643A (en) * | 2023-04-03 | 2023-07-07 | 嘉兴纳科新材料有限公司 | Acid and alkali resistant conductive coating composite metal electrode plate and preparation method thereof |
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| CN102020780A (en) * | 2010-11-24 | 2011-04-20 | 沈阳工业大学 | Method for preparing all-solid-state polymer electrolyte membrane and prepared electrolyte membrane |
| CN102468490A (en) * | 2010-11-19 | 2012-05-23 | 中国科学院金属研究所 | Surface chromium carbide/graphite composite coating for vanadium redox flow battery stainless steel bipolar plate |
| KR20160007719A (en) * | 2014-06-25 | 2016-01-21 | 주식회사 누리플랜 | Bipolar plate for redox flow battery |
| CN108336371A (en) * | 2018-02-05 | 2018-07-27 | 大连融科储能技术发展有限公司 | A kind of bipolar plates used for all-vanadium redox flow battery |
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Patent Citations (4)
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| CN102468490A (en) * | 2010-11-19 | 2012-05-23 | 中国科学院金属研究所 | Surface chromium carbide/graphite composite coating for vanadium redox flow battery stainless steel bipolar plate |
| CN102020780A (en) * | 2010-11-24 | 2011-04-20 | 沈阳工业大学 | Method for preparing all-solid-state polymer electrolyte membrane and prepared electrolyte membrane |
| KR20160007719A (en) * | 2014-06-25 | 2016-01-21 | 주식회사 누리플랜 | Bipolar plate for redox flow battery |
| CN108336371A (en) * | 2018-02-05 | 2018-07-27 | 大连融科储能技术发展有限公司 | A kind of bipolar plates used for all-vanadium redox flow battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114122422A (en) * | 2021-09-30 | 2022-03-01 | 哈尔滨工业大学（威海） | Preparation method of surface microstructure of bipolar plate of fuel cell |
| CN114122422B (en) * | 2021-09-30 | 2022-07-19 | 哈尔滨工业大学（威海） | Preparation method of surface microstructure of bipolar plate of fuel cell |
| CN116396643A (en) * | 2023-04-03 | 2023-07-07 | 嘉兴纳科新材料有限公司 | Acid and alkali resistant conductive coating composite metal electrode plate and preparation method thereof |
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Application publication date: 20190326 |