CN107039665A - A kind of preparation method of composite dual-electrode plates used for all-vanadium redox flow battery - Google Patents
A kind of preparation method of composite dual-electrode plates used for all-vanadium redox flow battery Download PDFInfo
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- CN107039665A CN107039665A CN201710127266.6A CN201710127266A CN107039665A CN 107039665 A CN107039665 A CN 107039665A CN 201710127266 A CN201710127266 A CN 201710127266A CN 107039665 A CN107039665 A CN 107039665A
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- flow battery
- electrode plates
- preparation
- redox flow
- carbon
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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention relates to flow battery technology field, more particularly to a kind of preparation method of composite dual-electrode plates used for all-vanadium redox flow battery.The present invention will be for two layers loose structure carbon/metal base up and down, centre folder macromolecule polymer material, by double roll compactions of heating into one block of compound conductive plastic plate；Then the composite plate both sides obtained by graphite felt/carbon felt being bonded by way of hot pressing again form final composite dual-electrode plates.The present invention had both met acidproof vanadium battery electrode plate, oxidative resistance, the requirement without sepage, and the intensity, specific surface area, electric conductivity of battery lead plate are added again, and reduced resistivity, and not only technique is simple, and processing cost is low, and the life-span is longer.
Description
（One）Technical field
The present invention relates to flow battery technology field, more particularly to a kind of preparation side of composite dual-electrode plates used for all-vanadium redox flow battery
Method.
（Two）Background technology
The advantage of all-vanadium flow battery is mainly manifested in：Self-discharge of battery very little；Discharge and recharge transformation efficiency is high；Energy is born in discharge and recharge
Power is strong, can repeatedly depth discharge and recharge, be particularly suitable for use in needing the occasion of quick charge and heavy-current discharge；Clean and safe is without dirt
Dye, is a kind of preferable green battery, meets modern environment protection conception.All-vanadium flow battery is usually used in stablizing solar energy, wind
The output of the regenerative resources such as energy, solves the problem of they are difficult to grid-connected because fluctuation is big, unstable；It is big for power system
Scale energy storage, cuts paddy and fills out peak, load power balance；Power quality management is controlled；Can be additionally used in important department equipment UPS and
Emergency Power etc..
Requirement of the all-vanadium flow battery to electrode must possess following characteristics：Electro-chemical activity is good, powerful oxidation corrosion resistance and strong acid
Property, conduct electricity very well and the features such as high mechanical strength.So far, electrode material used is mainly metal electrode, with stone
Black felt, carbon felt and graphite-carbon composite are the carbon pole and compound conductive plastic electrode of representative.Research shows metal electrode
Cost is too high, invertibity is poor, be used for a long time after be easily passivated, reduction battery performance；And conductive plastics electrode resistance rate
It is larger；Carbon pole relative price is cheap, reliability is high, operation and maintenance expense is all relatively low, but for a long time at higher current densities
Easily etch, therefore battery performance is restricted, how to obtain that stability is good, resistivity is low, electro-chemical activity good, cost
Low electrode, has become the critical aspects of vanadium cell system research and development.
（Three）The content of the invention
The present invention in order to make up the deficiencies in the prior art there is provided a kind of stability is good, resistivity is low, electro-chemical activity good, into
The preparation method of this low composite dual-electrode plates used for all-vanadium redox flow battery.
The present invention is achieved through the following technical solutions：
A kind of preparation method of composite dual-electrode plates used for all-vanadium redox flow battery, comprises the following steps：
（1）Flat board is made in macromolecule polymer material, be placed in above and below between two layers of loose structure carbon/metal base, obtain
Composite construction；
（2）By step（1）In obtained composite construction carry out roll-in by double rolls of heating, obtain compound conductive plastic plate；
（3）It is washed with deionized water only, is then put into Muffle furnace, in 180- after graphite felt/carbon felt is put into processing in concentrated sulfuric acid
4-6h is toasted at 300 DEG C and takes out stand-by；
（4）Graphite felt/carbon felt is laid in both sides respectively above and below compound conductive plastic plate, is positioned over together in mould, is heated to
100-150 DEG C, film is closed from both direction pressure up and down, final integrated bipolar plates are obtained.
Two layers up and down is loose structure carbon/metal base, centre folder macromolecule polymer material, by adding by the present invention
Double roll compactions of heat are into one block of compound conductive plastic plate；Then again by way of hot pressing graphite felt/carbon felt bonding gained
To composite plate both sides form final composite dual-electrode plates.In the present invention, loose structure carbon/metal base is not only in the plastic
Conductive network is formed, and forms the mechanical strength that skeleton greatly strengthen bipolar plates.
Its preferred technical scheme is：
Step（1）In, macromolecule polymer material be polyethylene, polypropylene, polyvinyl chloride, polyacrylonitrile, nylon, polypyrrole,
One or more in makrolon and polyaniline.
Loose structure carbon/metal base is graphite felt, carbon felt, carbon fiber paper, carbon cloth, foam copper or nickel foam.
The mass ratio of macromolecule polymer material and loose structure carbon/metal base is 60-90%：40-10%.
Step（2）In, composite construction is with 3-10m/h speed by being heated to 130-180 DEG C of double rolls.
Step（3）In, the thickness of graphite felt/carbon felt is 3-8mm, and the mass concentration of the concentrated sulfuric acid is 70-98%, graphite felt/carbon
Felt handles 4-8h in concentrated sulfuric acid.
Step（4）In, conjunction film pressure is 30-50MPa, and the retention time is 0-30min.
The present invention had both met acidproof vanadium battery electrode plate, oxidative resistance, the requirement without sepage, and the strong of battery lead plate is added again
Degree, specific surface area, electric conductivity, and resistivity is reduced, not only technique is simple, and processing cost is low, and the life-span is longer.
（Four）Brief description of the drawings
The present invention is further illustrated below in conjunction with the accompanying drawings.
Fig. 1 is the preparing processes schematic diagram of composite plate of the present invention；
Fig. 2 is the structural representation of bipolar plates of the present invention.
In figure, 1 macromolecule polymer material, 2 loose structure carbons/metal base, 3 composite plates, 4 pairs of rolls, 5 graphite
Felt/carbon felt.
（Five）Embodiment
Below in conjunction with accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described.
Embodiment 1：
A kind of composite dual-electrode plates used for all-vanadium redox flow battery, are prepared by following methods：
（1）PE modified plastics and 1mm nickel foam are pressed into certain weight ratio 70%：30% is configured, and by poly- second
2mm flat board is made in alkene modified plastics, be placed in above and below between two layers of foam nickel；
（2）By step（1）In press from both sides PE modified plastic plate between obtained two layers of foam nickel heating passed through with 3m/h speed
To 130 DEG C of double rolls, one block of compound conductive plastic plate is obtained；
（3）3mm graphite felt for vanadium cell is placed on to handle in 70% concentrated sulfuric acid and is washed with deionized water after 8h only, is then put into
In Muffle furnace, take out stand-by after baking 6h at temperature is 180 DEG C；
（4）PE modified composite panel of plastic material is positioned in the fixture of customization, then two panels 3mm graphite felts and polyethylene changed
Property composite panel of plastic material, be positioned in the mould of customization, be heated to 100 DEG C of temperature, from up and down both direction with 50MPa pressure
Matched moulds, keeps 30min, make above and below two panels graphite felt be adhered to the both sides of composite plate, obtain final integrated bipolar plates.
Embodiment 2：
A kind of composite dual-electrode plates used for all-vanadium redox flow battery, are prepared by following methods：
（1）Polycarbonate modified plastics and 1mm graphite felt are pressed into certain weight ratio 80%：20% is configured, and will be poly-
2mm flat board is made in carbonate-modified plastics, be placed in above and below between two layers of graphite felt；
（2）By step（1）In press from both sides polycarbonate modified plastic plate with 5m/h speed by adding between obtained two layers of graphite felt
Heat obtains one block of compound conductive plastic plate to 150 DEG C of double rolls；；
（3）8mm graphite felt for vanadium cell is placed on to handle in 98% concentrated sulfuric acid and is washed with deionized water after 4h only, is then put into
In Muffle furnace, take out stand-by after baking 5h at temperature is 240 DEG C；
（4）Polycarbonate modified composite panel of plastic material is positioned in the fixture of customization, then two panels 8mm graphite felts and poly- carbonic acid
Ester modified composite panel of plastic material, is positioned in the mould of customization, is heated to 120 DEG C of temperature, from both direction up and down with 40MPa's
Pressure matched moulds, keeps 20min, make above and below two panels graphite felt be adhered to the both sides of composite plate, obtain final integrated bipolar plates.
Embodiment 3：
A kind of composite dual-electrode plates used for all-vanadium redox flow battery, are prepared by following methods：
（1）Polyaniline-modified plastics and 1mm carbon fiber paper are pressed into certain weight ratio 90%：10% is configured, and will be poly-
2mm flat board is made in aniline modified plastics, be placed in above and below between two layers of carbon fiber paper；
（2）By step（1）In press from both sides polyaniline-modified plastic plate with 10m/h speed by adding between obtained two layers of carbon fiber paper
Heat obtains one block of compound conductive plastic plate to 180 DEG C of double rolls；；
（3）6mm graphite felt for vanadium cell is placed on to handle in 80% concentrated sulfuric acid and is washed with deionized water after 6h only, is then put into
In Muffle furnace, take out stand-by after baking 4h at temperature is 300 DEG C；
（4）Polyaniline-modified composite panel of plastic material is positioned in the fixture of customization, then two panels 6mm graphite felts and polyaniline changed
Property composite panel of plastic material, be positioned in the mould of customization, be heated to 150 DEG C of temperature, from up and down both direction with 30MPa pressure
Matched moulds, keeps 10min, make above and below two panels graphite felt be adhered to the both sides of composite plate, obtain final integrated bipolar plates.
The method for production for the bipolar plates used for all-vanadium redox flow battery that the present invention is provided, using macromolecule polymer material and porous
Structure carbon/metal base, composite dual-electrode plates made from the method extruded by hot roll have low-resistivity, highly conductive characteristic
Composite, specific insulation is in below 1.0 Ω cm after testing.The spy of its existing high polymer material corrosion resistance and durability
Property, again low with cost in preparation process, the characteristic of easy-formation, the 5kw all-vanadium flow battery piles assembled with the present invention exist
40mA/cm2Under electric current is close, charge-discharge performance is current efficiency 90%, and voltage efficiency is 80%, and energy efficiency 80%, electrolyte is utilized
Rate 85%.Compared with prior art, the preparation method for the composite dual-electrode plates used for all-vanadium redox flow battery that the present invention is provided, more with conduction
Porous materials are matrix, form conductive network, integrated bipolar plates are fabricated to by the method for impregnating molding, so as to reduce graphite
The contact resistance of felt/between carbon felt and conductive plate, to meet the requirement of bipolar plates used for all-vanadium redox flow battery.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (7)
1. a kind of preparation method of composite dual-electrode plates used for all-vanadium redox flow battery, it is characterized in that, comprise the following steps：（1）By high score
Flat board is made in sub- polymeric material, be placed in above and below between two layers of loose structure carbon/metal base, obtain composite construction；（2）Will
Step（1）In obtained composite construction carry out roll-in by double rolls of heating, obtain compound conductive plastic plate；（3）By graphite
Felt/carbon felt, which is put, to be washed with deionized water net after processing in concentrated sulfuric acid, be then put into Muffle furnace, in toasting 4- at 180-300 DEG C
6h takes out stand-by；（4）Graphite felt/carbon felt is laid in both sides respectively above and below compound conductive plastic plate, is positioned over together in mould, plus
Heat closes film from both direction pressure up and down, obtains final integrated bipolar plates to 100-150 DEG C.
2. the preparation method of composite dual-electrode plates used for all-vanadium redox flow battery according to claim 1, it is characterised in that：Step
（1）In, macromolecule polymer material is polyethylene, polypropylene, polyvinyl chloride, polyacrylonitrile, nylon, polypyrrole, makrolon
With the one or more in polyaniline.
3. the preparation method of composite dual-electrode plates used for all-vanadium redox flow battery according to claim 1, it is characterised in that：Step
（1）In, loose structure carbon/metal base is graphite felt, carbon felt, carbon fiber paper, carbon cloth, foam copper or nickel foam.
4. the preparation method of composite dual-electrode plates used for all-vanadium redox flow battery according to claim 1, it is characterised in that：Step
（1）In, the mass ratio of macromolecule polymer material and loose structure carbon/metal base is 60-90%：40-10%.
5. the preparation method of composite dual-electrode plates used for all-vanadium redox flow battery according to claim 1, it is characterised in that：Step
（2）In, composite construction is with 3-10m/h speed by being heated to 130-180 DEG C of double rolls.
6. the preparation method of composite dual-electrode plates used for all-vanadium redox flow battery according to claim 1, it is characterised in that：Step
（3）In, the thickness of graphite felt/carbon felt is 3-8mm, and the mass concentration of the concentrated sulfuric acid is 70-98%, and graphite felt/carbon felt is in concentrated sulfuric acid
Handle 4-8h.
7. the preparation method of composite dual-electrode plates used for all-vanadium redox flow battery according to claim 1, it is characterised in that：Step
（4）In, conjunction film pressure is 30-50MPa, and the retention time is 0-30min.
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| CN201710127266.6A CN107039665A (en) | 2017-03-06 | 2017-03-06 | A kind of preparation method of composite dual-electrode plates used for all-vanadium redox flow battery |
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| CN201710127266.6A CN107039665A (en) | 2017-03-06 | 2017-03-06 | A kind of preparation method of composite dual-electrode plates used for all-vanadium redox flow battery |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108134106A (en) * | 2018-01-10 | 2018-06-08 | 保定百能汇通新能源科技有限公司 | A kind of compound bipolar plates and preparation method thereof |
| CN108598519A (en) * | 2018-05-18 | 2018-09-28 | 深圳市晶特智造科技有限公司 | A kind of bipolar plates and preparation method thereof |
| CN109728318A (en) * | 2017-10-30 | 2019-05-07 | 中国科学院金属研究所 | A kind of vanadium cell highly conductive bipolar plates and its continuous processing device and method |
| CN109728319A (en) * | 2017-10-30 | 2019-05-07 | 中国科学院金属研究所 | A kind of bipolar plate of vanadium cell and its continuous processing device and method |
| CN110676479A (en) * | 2018-07-03 | 2020-01-10 | 河北金雕新材料科技有限公司 | Full-vanadium redox flow battery bipolar plate and preparation method thereof |
| CN111584895A (en) * | 2020-05-25 | 2020-08-25 | 广州市香港科大霍英东研究院 | Oriented ordered electrode and preparation method and application thereof |
| CN113782751A (en) * | 2021-09-17 | 2021-12-10 | 宁波信远炭材料股份有限公司 | Preparation method of high-flexibility carbon/resin composite material |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109728318A (en) * | 2017-10-30 | 2019-05-07 | 中国科学院金属研究所 | A kind of vanadium cell highly conductive bipolar plates and its continuous processing device and method |
| CN109728319A (en) * | 2017-10-30 | 2019-05-07 | 中国科学院金属研究所 | A kind of bipolar plate of vanadium cell and its continuous processing device and method |
| CN109728319B (en) * | 2017-10-30 | 2021-10-22 | 中国科学院金属研究所 | Bipolar plate for vanadium battery and continuous processing device and method thereof |
| CN109728318B (en) * | 2017-10-30 | 2021-10-22 | 中国科学院金属研究所 | High-conductivity bipolar plate for vanadium battery and continuous processing device and method thereof |
| CN108134106A (en) * | 2018-01-10 | 2018-06-08 | 保定百能汇通新能源科技有限公司 | A kind of compound bipolar plates and preparation method thereof |
| CN108598519A (en) * | 2018-05-18 | 2018-09-28 | 深圳市晶特智造科技有限公司 | A kind of bipolar plates and preparation method thereof |
| CN110676479A (en) * | 2018-07-03 | 2020-01-10 | 河北金雕新材料科技有限公司 | Full-vanadium redox flow battery bipolar plate and preparation method thereof |
| CN111584895A (en) * | 2020-05-25 | 2020-08-25 | 广州市香港科大霍英东研究院 | Oriented ordered electrode and preparation method and application thereof |
| CN113782751A (en) * | 2021-09-17 | 2021-12-10 | 宁波信远炭材料股份有限公司 | Preparation method of high-flexibility carbon/resin composite material |
| CN113782751B (en) * | 2021-09-17 | 2023-08-11 | 宁波信远材料科技股份有限公司 | Preparation method of high-flexibility carbon/resin composite material |
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Application publication date: 20170811 |