CN106848346A - Flow battery bipolar plates and preparation method thereof - Google Patents
Flow battery bipolar plates and preparation method thereof Download PDFInfo
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- CN106848346A CN106848346A CN201710127267.0A CN201710127267A CN106848346A CN 106848346 A CN106848346 A CN 106848346A CN 201710127267 A CN201710127267 A CN 201710127267A CN 106848346 A CN106848346 A CN 106848346A
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- bipolar plates
- flow battery
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- felt
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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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Cell Electrode Carriers And Collectors (AREA)
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Abstract
The present invention relates to flow battery technology field, more particularly to a kind of flow battery bipolar plates and preparation method thereof.The flow battery bipolar plates, it is characterised in that：The bipolar plates are composited by five-layer structure successively from down to up, respectively graphite felt/carbon felt, loose structure carbon/metal base, macromolecule polymer material, loose structure carbon/metal base, graphite felt/carbon felt.Present invention process is simple, low manufacture cost, long service life meets several classes of resistance to sours of all-vanadium flow battery, ne-leakage, intensity high, pliability and tensile property is good, electric conductivity is good requirement, intensity, specific surface area, the electric conductivity of battery lead plate are increased, and reduces resistivity.
Description
（One）Technical field
The present invention relates to flow battery technology field, more particularly to a kind of flow battery bipolar plates and preparation method thereof.
（Two）Background technology
All-vanadium flow battery is a kind of extensive energy storage technology.When wind energy, Solar lamp renewable energy power generation large-scale grid connection
When using, " dump energy " or supplement " power shortage " can be quickly absorbed using all-vanadium flow battery.By all-vanadium flow battery
Used cooperatively with wind-force and photovoltaic generating system, not only overcome wind-powered electricity generation and photovoltaic fluctuation and intermittence is brought not to power network
Profit influence, so as to ensure that the stability of operation of power networks, can provide reactive power support for power network again, the raising quality of power supply, can be with
Effective regulation and the voltage and frequency of control system, the electric energy of the non-scheduling for being become schedulable, promote to a certain extent
The development of wind-powered electricity generation and photovoltaic industry is entered.
Bipolar plates requirement chemical stability is good, and high mechanical strength, impermeability is good, low cost of manufacture and long working life.
What current all-vanadium flow battery was used is generally graphite cake and carbon mould plate.The advantage of graphite cake is conductance high, and impermeability is good, tool
There is certain mechanical strength；But, graphite cake there is also some shortcomings, such as sealing is poor, due to technique manufacture limitation, greatly
The graphite cake manufacture difficulty of size is big, bad mechanical property, and weight is big, high cost, under long-term high current density use, graphite cake table
Face occurs the phenomenon of corrosion.The advantage of conductive plastic plate is good, easy lightweight, large scale low manufacture cost, chemical stability
In sealing；But plastic plate is big with the contact resistance of carbon felt, electrical conductivity is low compared to graphite cake.
（Three）The content of the invention
The present invention is in order to make up the deficiencies in the prior art, there is provided a kind of corrosion-resistant, intensity is high, good conductivity flow battery is used
Bipolar plates and preparation method thereof.
The present invention is achieved through the following technical solutions：
A kind of flow battery bipolar plates, it is characterised in that：The bipolar plates are composited by five-layer structure successively from down to up,
Respectively graphite felt/carbon felt, loose structure carbon/metal base, macromolecule polymer material, loose structure carbon/Metal Substrate
Material, graphite felt/carbon felt.
More excellent technical scheme of the invention is：
Loose structure carbon/the metal base is graphite felt, carbon felt, carbon fiber paper, carbon cloth, foam copper or nickel foam.
The macromolecule polymer material is polyethylene, polypropylene, polyvinyl chloride, polyacrylonitrile, nylon, polypyrrole, poly-
One or more in carbonic ester and polyaniline.
The preparation method of flow battery bipolar plates of the present invention, comprises the following steps：
（1）Macromolecule polymer material is made flat board, is placed between upper and lower two-layer loose structure carbon/metal base, obtained
Composite construction；
（2）By step（1）The composite construction for obtaining is put into the mould for being pre-heated to 80-120 DEG C, closes upper and lower grinding tool, then
Mold temperature is risen to 120-180 DEG C, 10-30min is incubated；
（3）Grinding tool is cooled to 50-80 DEG C, grinding tool is opened, macromolecule polymer material composite plate is taken out；
（4）Graphite felt/carbon felt is put and is processed in concentrated sulfuric acid, be then washed with deionized water only, be placed in Muffle furnace, in 180-
Take out stand-by after toasting 4-6h at 300 DEG C；
（5）Composite plate is placed in fixture, two panels graphite felt/carbon felt is laid on composite plate upper and lower surface, be placed in grinding tool, plus
To 100-150 DEG C, pressure closes film to heat, obtains integrated bipolar panel products.
Bipolar plates of the invention are made up of five-layer structure altogether, and its preparation is divided into two steps：1. by the side of golden type matrix pressure
Method synthesizes upper and lower two-layer for loose structure carbon/metal base, intermediate course are the composite plate of macromolecule polymer material；2. lead to
Graphite felt/carbon felt golden tooth is formed final integrated bipolar plates by the mode for crossing hot pressing in the composite plate both sides of step 1 gained.This
Loose structure carbon/metal base not only forms conductive network in the plastic in invention, and formed skeleton greatly strengthen it is double
The mechanical strength of pole plate.
Its preferred technical scheme is：
Step（1）In, the mass ratio of macromolecule polymer material and loose structure carbon/metal base is 60-90%：40-10%.
Step（2）In, after closure upper/lower die, mold temperature is 120-180 DEG C, and pressure is insulation under 30-50MPa.
Step（3）In, mould cooling means is that liquid nitrogen is cooled down or cooling water cooling.
Step（4）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 process time in concentrated sulfuric acid is 4-8h.
Step（5）In, conjunction film pressure is 30-50MPa, and the retention time is 0-30min.
Present invention process is simple, and low manufacture cost, long service life meets all-vanadium flow battery several classes of resistance to sours, nothings
Seepage, intensity are high, pliability and tensile property is good, electric conductivity is good requirement, increased the intensity of battery lead plate, specific surface area,
Electric conductivity, and reduce resistivity.
（Four）Brief description of the drawings
The present invention is further illustrated below in conjunction with the accompanying drawings.
Fig. 1 is the structural representation of composite construction of the present invention；
Fig. 2 is the machining state schematic diagram of composite construction of the present invention；
Fig. 3 is the structural representation of composite plate of the present invention；
Fig. 4 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 molds, 5 times moulds
Tool, 6 graphite felts/carbon felt.
（Five）Specific 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 flow battery bipolar plates, are prepared by following methods：
（1）The nickel foam of PE modified plastics and 1mm is compared 70% by certain weight：30% is configured, and by poly- second
Alkene modified plastics is made the flat board of 2mm, is placed between upper and lower two layers of foam nickel；
（2）By step（1）In press from both sides the pre-add that PE modified plastic plate is put into customization together between the two layers of foam nickel that obtains
Heat is in 120 DEG C of mould；Closure upper/lower die, is then heated to 150 DEG C, and keeping temperature by mold temperature, applies
The pressure of 30MPa continues 20min；
（3）By step（2）In mould be cooled to 80 DEG C, open mould, take out PE modified composite panel of plastic material；
（4）The graphite felt for vanadium cell of 6mm is placed on after processing 8h in 70% concentrated sulfuric acid and be washed with deionized water only, be then put into
In Muffle furnace, take out stand-by after toasting 4h at being 300 DEG C in temperature；
（5）PE modified composite panel of plastic material is positioned in the fixture of customization, then two panels 6mm graphite felts and polyethylene are changed
Property composite panel of plastic material, is positioned in the mould of customization, 150 DEG C of temperature is heated to, from upper and lower both direction with the pressure of 30MPa
Matched moulds, keeps 10min, upper and lower two panels graphite felt is adhered to the both sides of composite plate, obtains final integrated bipolar plates.
Embodiment 2：
A kind of flow battery bipolar plates, are prepared by following methods：
（1）The carbon felt of modified polyacrylonitrile plastics and 1mm is compared 80% by certain weight：20% is configured, and by poly- third
Alkene nitrile modified plastics is made the flat board of 2mm, is placed between upper and lower two-layer carbon felt；
（2）By step（1）In press from both sides the pre-add that modified polyacrylonitrile plastic plate is put into customization together between the two-layer carbon felt that obtains
Heat is in 100 DEG C of mould.Closure upper/lower die, is then heated to 180 DEG C, and keeping temperature by mold temperature, applies
The pressure of 40MPa continues 10min；
（3）By step（2）In mould be cooled to 60 DEG C, open mould, take out PE modified composite panel of plastic material；
（4）The graphite felt for vanadium cell of 8mm is placed on after processing 6h in 80% concentrated sulfuric acid and be washed with deionized water only, be then put into
In Muffle furnace, take out stand-by after toasting 6h at being 180 DEG C in temperature；
（5）Modified polyacrylonitrile composite panel of plastic material is positioned in the fixture of customization, then two panels 8mm graphite felts and polypropylene
Nitrile modified plastics composite plate, is positioned in the mould of customization, is heated to 100 DEG C of temperature, from upper and lower both direction with 50MPa's
Pressure matched moulds, keeps 30min, upper and lower two panels graphite felt is adhered to the both sides of composite plate, obtains final integrated bipolar plates.
Embodiment 3：
A kind of flow battery bipolar plates, are prepared by following methods：
（1）The foam copper of polypyrrole modified plastics and 1mm is compared 80% by certain weight：20% is configured, and by poly- pyrrole
The flat board that modified plastics is made 2mm is coughed up, is placed between upper and lower two layers of foam copper；
（2）By step（1）In press from both sides the pre-add that polypyrrole modified plastics plate is put into customization together between the two layers of foam copper that obtains
Heat is in 80 DEG C of mould.Closure upper/lower die, is then heated to 120 DEG C, and keeping temperature by mold temperature, applies
The pressure of 50MPa continues 30min；
（3）By step（2）In mould be cooled to 70 DEG C, open mould, take out PE modified composite panel of plastic material；
（4）The vanadium cell carbon felt of 5mm is placed on after processing 4h in 90% concentrated sulfuric acid and be washed with deionized water only, be then put into horse
Not in stove, take out stand-by after toasting 5h at being 240 DEG C in temperature；
（5）Polypyrrole modified plastics composite plate is positioned in the fixture of customization, then two panels 6mm carbon felts and polypyrrole are modified
Composite panel of plastic material, is positioned in the mould of customization, is heated to 120 DEG C of temperature, is closed with the pressure of 40MPa from upper and lower both direction
Mould, keeps 20min, upper and lower two panels carbon felt is adhered to the both sides of composite plate, obtains final integrated bipolar plates.
The preparation method of 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, has low-resistivity, high connductivity characteristic by composite dual-electrode plates obtained in impregnating the method for molding
Composite, specific insulation is in below 1.0 Ω cm after testing.The spy of its existing macromolecular material corrosion resistance and durability
Property, there is low cost again in preparation process, the characteristic of easy-formation is existed with the 5kw all-vanadium flow battery piles of present invention assembling
40mA/cm2Under electric current is close, charge-discharge performance is current efficiency 90%, and 80%, energy efficiency 80%, electrolyte is utilized voltage efficiency
Rate 85%.Compared with prior art, the preparation method of 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 uses the present invention.
Various 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, the present 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 scope most wide for causing.
Claims (9)
1. a kind of flow battery bipolar plates, it is characterised in that：The bipolar plates be combined by five-layer structure successively from down to up and
Into respectively graphite felt/carbon felt, loose structure carbon/metal base, macromolecule polymer material, loose structure carbon/metal
Base material, graphite felt/carbon felt.
2. flow battery bipolar plates according to claim 1, it is characterised in that：Loose structure carbon/the Metal Substrate
Material is graphite felt, carbon felt, carbon fiber paper, carbon cloth, foam copper or nickel foam.
3. flow battery bipolar plates according to claim 1, it is characterised in that：The macromolecule polymer material is poly-
One or more in ethene, polypropylene, polyvinyl chloride, polyacrylonitrile, nylon, polypyrrole, makrolon and polyaniline.
4. the preparation method of flow battery bipolar plates according to claim 1, it is characterized by, comprise the following steps：（1）
Macromolecule polymer material is made flat board, is placed between upper and lower two-layer loose structure carbon/metal base, obtain composite junction
Structure；（2）By step（1）The composite construction for obtaining is put into the mould for being pre-heated to 80-120 DEG C, closes upper and lower grinding tool, then will
Mold temperature rises to 120-180 DEG C, is incubated 10-30min；（3）Grinding tool is cooled to 50-80 DEG C, grinding tool is opened, macromolecule is taken out
Polymeric material composite plate；（4）Graphite felt/carbon felt is put and is processed in concentrated sulfuric acid, be then washed with deionized water only, be placed in Muffle
In stove, take out stand-by after 4-6h is toasted at 180-300 DEG C；（5）Composite plate is placed in fixture, by two panels graphite felt/carbon felt
Composite plate upper and lower surface is laid on, is placed in grinding tool, be heated to 100-150 DEG C, pressure closes film, obtained integrated bipolar plates and produce
Product.
5. the preparation method of flow battery bipolar plates according to claim 4, it is characterised in that：Step（1）In, high score
The mass ratio of sub- polymeric material and loose structure carbon/metal base is 60-90%：40-10%.
6. the preparation method of flow battery bipolar plates according to claim 4, it is characterised in that：Step（2）In, closure
After upper/lower die, mold temperature is 120-180 DEG C, and pressure is insulation under 30-50MPa.
7. the preparation method of flow battery bipolar plates according to claim 4, it is characterised in that：Step（3）In, mould
Cooling means is that liquid nitrogen is cooled down or cooling water cooling.
8. the preparation method of flow battery bipolar plates according to claim 4, it is characterised in that：Step（4）In, graphite
The thickness of felt/carbon felt is 3-8mm, and the mass concentration of the concentrated sulfuric acid is 70-98%, graphite felt/carbon felt process time in concentrated sulfuric acid
It is 4-8h.
9. the preparation method of flow battery bipolar plates according to claim 4, it is characterised in that：Step（5）In, close film
Pressure is 30-50MPa, and the retention time is 0-30min.
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| CN201710127267.0A CN106848346B (en) | 2017-03-06 | 2017-03-06 | Flow battery bipolar plates and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107634238A (en) * | 2017-08-29 | 2018-01-26 | 国网电力科学研究院武汉南瑞有限责任公司 | A kind of bipolar plates and its manufacture method with higher-strength |
| 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 |
| CN109301278A (en) * | 2018-09-26 | 2019-02-01 | 苏州纳磐新材料科技有限公司 | A kind of bipolar plate material and its preparation method and application |
| CN109732943A (en) * | 2018-12-29 | 2019-05-10 | 苏州弗尔赛能源科技股份有限公司 | Bipolar plate for fuel cell and preparation method thereof |
| CN110993982A (en) * | 2019-11-27 | 2020-04-10 | 一汽解放汽车有限公司 | High-conductivity flexible graphite bipolar plate and preparation method thereof |
| CN111370719A (en) * | 2020-03-19 | 2020-07-03 | 辽宁科京新材料科技有限公司 | High-conductivity bipolar plate for flow battery and continuous processing device and 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 |
| CN112687906A (en) * | 2020-12-28 | 2021-04-20 | 大连博融新材料有限公司 | Multi-layer composite bipolar plate with flow channels, production method and application thereof |
| CN115411278A (en) * | 2022-10-13 | 2022-11-29 | 北京阳光鸿志电气工程技术有限公司 | Method for improving corrosion resistance of graphite bipolar plate |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107634238A (en) * | 2017-08-29 | 2018-01-26 | 国网电力科学研究院武汉南瑞有限责任公司 | A kind of bipolar plates and its manufacture method with higher-strength |
| CN107634238B (en) * | 2017-08-29 | 2024-03-15 | 国网电力科学研究院武汉南瑞有限责任公司 | Bipolar plate with higher strength and manufacturing 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 |
| CN109301278A (en) * | 2018-09-26 | 2019-02-01 | 苏州纳磐新材料科技有限公司 | A kind of bipolar plate material and its preparation method and application |
| CN109732943A (en) * | 2018-12-29 | 2019-05-10 | 苏州弗尔赛能源科技股份有限公司 | Bipolar plate for fuel cell and preparation method thereof |
| CN110993982A (en) * | 2019-11-27 | 2020-04-10 | 一汽解放汽车有限公司 | High-conductivity flexible graphite bipolar plate and preparation method thereof |
| CN111370719A (en) * | 2020-03-19 | 2020-07-03 | 辽宁科京新材料科技有限公司 | High-conductivity bipolar plate for flow battery and continuous processing device and 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 |
| CN112687906A (en) * | 2020-12-28 | 2021-04-20 | 大连博融新材料有限公司 | Multi-layer composite bipolar plate with flow channels, production method and application thereof |
| CN112687906B (en) * | 2020-12-28 | 2022-05-13 | 大连博融新材料有限公司 | Multi-layer composite bipolar plate with flow channels, production method and application thereof |
| CN115411278A (en) * | 2022-10-13 | 2022-11-29 | 北京阳光鸿志电气工程技术有限公司 | Method for improving corrosion resistance of graphite bipolar plate |
| CN115411278B (en) * | 2022-10-13 | 2024-09-20 | 北京阳光鸿志电气工程技术有限公司 | Method for improving corrosion resistance of graphite bipolar plate |
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| Publication number | Publication date |
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| CN106848346B (en) | 2019-07-26 |
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