CN117885267A - Flow battery bipolar plate, preparation method thereof and all-vanadium flow battery - Google Patents
Flow battery bipolar plate, preparation method thereof and all-vanadium flow battery Download PDFInfo
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- CN117885267A CN117885267A CN202410155513.3A CN202410155513A CN117885267A CN 117885267 A CN117885267 A CN 117885267A CN 202410155513 A CN202410155513 A CN 202410155513A CN 117885267 A CN117885267 A CN 117885267A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 20
- 238000003825 pressing Methods 0.000 claims abstract description 103
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 86
- 239000010439 graphite Substances 0.000 claims abstract description 86
- 239000011347 resin Substances 0.000 claims abstract description 72
- 229920005989 resin Polymers 0.000 claims abstract description 72
- 239000000843 powder Substances 0.000 claims abstract description 53
- 238000000465 moulding Methods 0.000 claims abstract description 40
- 238000007731 hot pressing Methods 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 238000007493 shaping process Methods 0.000 claims abstract description 22
- 238000003892 spreading Methods 0.000 claims abstract description 20
- 230000007480 spreading Effects 0.000 claims abstract description 20
- 238000007664 blowing Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 31
- 230000001007 puffing effect Effects 0.000 claims description 27
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052754 neon Inorganic materials 0.000 claims description 4
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000523 sample Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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 invention disclosesA flow battery bipolar plate, a preparation method thereof and an all-vanadium flow battery are provided. A preparation method of a flow battery bipolar plate comprises the following steps: (1) Expanding expandable graphite particles by a bulking furnace at high temperature to obtain graphite worms; (2) Respectively mixing graphite worms and resin powder according to the mass ratio of (70-95): (30-5) blowing into an airflow disperser, and fully and uniformly mixing to obtain a mixture of resin and graphite worms; (3) The mixture of resin and graphite worms is mixed according to the surface density of 1000g/m to 2000g/m 2 Filling to form a spreading material, and pre-pressing the spreading material to obtain a pre-pressing plate; (4) hot-press molding the pre-pressed plate to obtain a hot-pressed plate; (5) cold-pressing and shaping the hot-pressing plate to obtain the bipolar plate. The invention has the following beneficial effects: 1. the energy consumption is reduced, and the production cost is reduced; 2. the dispersing effect of the resin and graphite worms is improved; 3. the flexibility strength and the flatness of the bipolar plate are ensured.
Description
Technical Field
The invention belongs to the technical field of flow battery bipolar plate materials, and provides a flow battery bipolar plate, a preparation method thereof and an all-vanadium flow battery.
Background
The all-vanadium redox flow battery has the advantages of intrinsic safety, long service life, recyclable electrolyte, no limitation of geographical conditions and the like, and can be applied to differentiated and diversified user side energy storage and high-safety, large-scale, medium-long-time centralized energy storage on the power supply/power grid side.
The all-vanadium redox flow battery mainly comprises electrolyte, an electrode, a selective proton exchange membrane, a bipolar plate and a current collector, wherein: the bipolar plate is used as one of key materials of the all-vanadium redox flow battery, plays a role in separating positive and negative electrolyte of two adjacent single cells, collecting current and supporting electrodes in a stacking structure of the electric pile, so that a plurality of single cells are connected in series in the electric pile, and the electric pile is required to have good gas resistance, liquid resistance, conductivity, oxidation resistance, acid corrosion resistance, mechanical strength and the like.
The conductivity of the bipolar plate comprises self body resistance and contact resistance, and the contact resistance between the bipolar plate/carbon felt and the bipolar plate/copper current collector accounts for 15-20% of the total resistance of the battery, so that the contact resistance between the bipolar plate and the carbon felt and the contact resistance between the bipolar plate and the contact resistance of the bipolar plate/copper current collector are ensured to be as low as possible in the whole life cycle, and the voltage efficiency, the cycle life and the power density of the battery are improved. The smaller the resistance of the bipolar plate in the thickness direction is, the better the power density of the battery is.
The Chinese patent application CN 116014161A discloses an all-vanadium redox flow battery bipolar plate and a preparation method thereof, and the preparation method of the all-vanadium redox flow battery bipolar plate comprises the following steps: step 1, weighing the following components in parts by weight: 70-90 parts of graphite worms; 10-30 parts of resin; the particle size of the resin is smaller than the pore size of the graphite worms; step 2, heating and mixing the components to a temperature which is 20 ℃ higher than the melting temperature of the resin, spraying graphite worms and the resin into mixing equipment sequentially or simultaneously, and adhering the resin to the surfaces of worm fibers at the moment of contacting the graphite worms to prepare a mixed material; and 3, molding the bipolar plate. In the technical scheme, the method comprises the following steps: the resin powder mainly plays a role in binding graphite worms and increasing the plate mechanical strength of the bipolar plate. However, the above technical solution has the following disadvantages: 1. because of the density and size difference of graphite worms and resin, the two substances are not uniform in the mixing process, and are stored and transferred after being mixed, the two substances are separated, the dispersing effect is poor, and the conductivity and strength uniformity of the bipolar plate are affected. The melted resin can also generate bonding agglomeration, and the area with high resin content of the bipolar plate and the electrode contact resistance are higher, so that the voltage distribution of the electrode contacted with the bipolar plate in the battery stack is uneven, thereby affecting the performance of the whole battery; 2. the method needs to heat graphite worms and resin, and has high energy consumption.
Disclosure of Invention
The invention aims to: in order to solve the problem that the dispersion of graphite materials and resin in the preparation process of the bipolar plate is difficult to realize uniformity and the conductivity of the bipolar plate is not ideal, the invention provides a flow battery bipolar plate, a preparation method thereof and an all-vanadium flow battery.
The technical scheme is as follows: a preparation method of a flow battery bipolar plate comprises the following specific steps:
(1) Expanding expandable graphite particles by a bulking furnace at high temperature to obtain graphite worms;
(2) And (3) respectively mixing graphite worms obtained in the step (1) with resin powder according to the mass ratio of (70-95) by nitrogen or inert gas: (30-5) blowing into an airflow disperser, and fully and uniformly mixing to obtain a mixture of resin and graphite worms;
(3) Mixing the resin obtained in the step (2) and graphite worms according to the surface density of 1000-2000 g/m 2 Filling to form cuboid spreading materials, and pre-pressing the spreading materials by a roll squeezer or a die squeezer to obtain a pre-pressing plate;
(4) The pre-pressing plate is subjected to hot press molding through a roller press or a die press to obtain a hot pressing plate;
(5) And cold-pressing and shaping the hot pressing plate through a roller press or a die press to obtain the bipolar plate.
Further, the specific process parameters of the puffing treatment in the step (1) are as follows: the puffing temperature is 600-1000 ℃ and the puffing time is 1-50 s.
Further, the average particle diameter D50 of the expandable graphite in the step (1) is 50-300 um.
Further, the resin powder in the step (2) has an average particle diameter D50 of 1 to 100 μm, and/or
The resin powder is one or more of polyvinylidene fluoride powder, polytetrafluoroethylene powder, polyethylene powder and polypropylene powder.
Further, the inert gas in the step (2) is one or more of argon, helium and neon.
Further, in the step (2), the temperature in the dispersing chamber of the air flow disperser is controlled to be 150-250 ℃.
Further, in the step (2), the graphite worms account for 70 to 95 weight percent of the total mass of the graphite worms and the resin powder in the blowing air flow disperser, and the balance is the resin powder. In the step (2), the resin powder contacts with high-temperature graphite worms and is fused and adhered in the surface pores of the worms, so that a good mixing state of the resin and the graphite worms is ensured.
Further, the thickness of the pre-pressing plate in the step (3) is 1-10 mm.
Further, in the hot press molding step of step (4): pressing the pre-pressed plate into a hot pressing plate with the thickness of 0.5-2 mm by a roller press or a die press, wherein:
the hot pressing temperature is 120-250 ℃, the pre-pressing time is 1-10 min, and the pre-pressing pressure is 1-30 MPa.
Further, in the cold press shaping step of step (5):
pressing the hot-pressed plate into a bipolar plate with the thickness of 0.3-1.2 mm at room temperature through a roller press or a die press, wherein:
cold pressing for 1-10 min at 25-50 MPa, and/or
The density of the bipolar plate is 1.4-1.9 g/cm 3 。
A flow battery bipolar plate is prepared by any one of the preparation methods.
The all-vanadium redox flow battery comprises the redox flow battery bipolar plate.
The beneficial effects are that: the flow battery bipolar plate and the preparation method thereof disclosed by the invention have the following beneficial effects:
1. the method directly mixes the expanded graphite worms with the resin through air flow, and utilizes the waste heat of the expanded graphite worms to melt and adsorb the resin, thereby reducing energy consumption and production cost;
2. the resin is not required to be heated and melted by hot air, so that the agglomeration of the melted resin is avoided, the dispersion effect of the resin and graphite worms is improved, and the bipolar plate with high conductivity and high strength is obtained;
3. the method adopts the steps of prepressing molding, hot press molding and cold press shaping to press the bipolar plate, avoids the breaking and cracking of the bipolar plate in the pressing process, reduces the gas quantity in the bipolar plate and ensures the flexibility strength and the flatness of the bipolar plate.
Drawings
Fig. 1 is a flow chart of a method of preparing a flow battery bipolar plate according to the present disclosure.
Detailed Description
The following detailed description of specific embodiments of the invention.
The "range" disclosed herein is defined in terms of lower and upper limits, with the given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 10 to 50 are listed for a particular parameter, it is understood that ranges of 10 to 40 and 20 to 50 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4 and 2 to 5. In this application, unless otherwise indicated, the range of values "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is only a shorthand representation of a combination of these values.
All embodiments and alternative embodiments of the present application may be combined with each other to form new solutions, unless specifically stated otherwise.
All technical features and optional technical features of the present application may be combined with each other to form new technical solutions, unless specified otherwise.
All steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise indicated. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
Reference herein to "comprising" and "including" means open ended, as well as closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
Unless otherwise specified, the reaction is carried out under normal temperature and normal pressure conditions.
Unless otherwise indicated, all parts or percentages are parts or percentages by weight.
In the present invention, the materials used are all known materials, and are commercially available or synthesized by known methods.
In the present invention, the devices or apparatuses used are conventional devices or apparatuses known in the art, and are commercially available.
The thicknesses of the bipolar plates prepared in examples 1 to 7 and comparative examples 1 to 2 were all tested using a digital display micrometer;
the tensile strength of the bipolar plates prepared in examples 1 to 7 and comparative examples 1 to 2 is referred to the energy industry standard NB/T42007-2013, namely, a bipolar plate test method for an all-vanadium redox flow battery, wherein a rectangular material with the length of 70mm multiplied by 10mm is taken as a sample, the initial gauge length of the sample is 50mm, and the sample is stretched at a speed of 2mm/min for testing;
the conductivity of the bipolar plates prepared in examples 1 to 7 and comparative examples 1 to 2 were all tested by using a dual electrical four probe resistivity tester.
Example 1
A preparation method of a flow battery bipolar plate comprises the following specific steps:
(1) Expanding expandable graphite particles by a bulking furnace at high temperature to obtain graphite worms;
(2) Respectively mixing graphite worms and resin powder obtained in the step (1) according to a mass ratio of 85:15 blowing the mixture into an airflow disperser, and fully and uniformly mixing the mixture to obtain a mixture of resin and graphite worms;
(3) Mixing the resin obtained in the step (2) and graphite worms according to the surface density of 1500g/m 2 Packing formation lengthSpreading the square body, and pre-compacting and molding the spread material by a roller press to obtain a pre-pressing plate;
(4) The pre-pressing plate is subjected to hot press molding through a roller press to obtain a hot pressing plate;
(5) And cold-pressing and shaping the hot pressing plate through a roller press to obtain the bipolar plate.
Further, the specific process parameters of the puffing treatment in the step (1) are as follows: the puffing temperature is 800 ℃, and the puffing time is 20s.
Further, the average particle diameter D50 of the expandable graphite in the step (1) is 150um.
Further, the average particle diameter D50 of the resin powder in the step (2) is 20um;
the resin powder is polyvinylidene fluoride powder.
Further, the temperature in the dispersing chamber of the gas flow disperser in the step (2) is controlled at 180 ℃.
Further, the thickness of the pre-pressing plate in the step (3) is 5mm.
Further, in the hot press molding step of step (4): pressing the pre-pressed plate into a hot pressing plate with the thickness of 1mm by a roller press, wherein:
the hot pressing temperature is 170 ℃, the pre-pressing time is 5min, and the pre-pressing pressure is 10MPa.
Further, in the cold press shaping step of step (5):
the hot-pressed plate was pressed into a bipolar plate with a thickness of 0.82mm by a roll press at room temperature, wherein:
cold pressing time is 5min, cold pressing pressure is 35Mpa, and density of bipolar plate is 1.65g/cm 3 。
A flow battery bipolar plate is prepared by any one of the preparation methods.
The all-vanadium redox flow battery comprises the redox flow battery bipolar plate.
Example 2
A preparation method of a flow battery bipolar plate comprises the following specific steps:
(1) Expanding expandable graphite particles by a bulking furnace at high temperature to obtain graphite worms;
(2) Respectively mixing graphite worms and resin powder obtained in the step (1) according to a mass ratio of 90:10 blowing the mixture into an airflow disperser, and fully and uniformly mixing the mixture to obtain a mixture of resin and graphite worms;
(3) Mixing the resin obtained in the step (2) and graphite worms according to the surface density of 1500g/m 2 Filling to form cuboid spreading materials, and pre-pressing the spreading materials by a roll squeezer to obtain a pre-pressing plate;
(4) The pre-pressing plate is subjected to hot press molding through a roller press to obtain a hot pressing plate;
(5) And cold-pressing and shaping the hot pressing plate through a roller press to obtain the bipolar plate.
Further, the specific process parameters of the puffing treatment in the step (1) are as follows: the puffing temperature is 800 ℃, and the puffing time is 20s.
Further, the average particle diameter D50 of the expandable graphite in the step (1) is 150um.
Further, the average particle diameter D50 of the resin powder in the step (2) is 20um; the resin powder is polyvinylidene fluoride powder.
Further, the temperature in the dispersing chamber of the gas flow disperser in the step (2) is controlled at 180 ℃.
Further, the thickness of the pre-pressing plate in the step (3) is 5mm.
Further, in the hot press molding step of step (4): pressing the pre-pressed plate into a hot pressing plate with the thickness of 1mm by a roller press, wherein:
the hot pressing temperature is 170 ℃, the pre-pressing time is 1min, and the pre-pressing pressure is 30MPa.
Further, in the cold press shaping step of step (5):
the hot-pressed plate was pressed into a bipolar plate with a thickness of 0.85mm by a roll press at room temperature, wherein:
cold pressing time is 1min, cold pressing pressure is 50Mpa, and density of bipolar plate is 1.63g/cm 3 。
A flow battery bipolar plate is prepared by any one of the preparation methods.
The all-vanadium redox flow battery comprises the redox flow battery bipolar plate.
Example 3
A preparation method of a flow battery bipolar plate comprises the following specific steps:
(1) Expanding expandable graphite particles by a bulking furnace at high temperature to obtain graphite worms;
(2) Respectively mixing graphite worms and resin powder obtained in the step (1) according to a mass ratio of 95:5, blowing the mixture into an airflow disperser, and fully and uniformly mixing the mixture to obtain a mixture of resin and graphite worms;
(3) Mixing the resin obtained in the step (2) and graphite worms according to the surface density of 1500g/m 2 Filling to form cuboid spreading materials, and pre-pressing the spreading materials by a molding press to obtain a pre-pressing plate;
(4) The pre-pressing plate is subjected to hot press molding through a molding press to obtain a hot pressing plate;
(5) And cold-pressing and shaping the hot pressing plate through a molding machine to obtain the bipolar plate.
Further, the specific process parameters of the puffing treatment in the step (1) are as follows: the puffing temperature is 800 ℃, and the puffing time is 20s.
Further, the average particle diameter D50 of the expandable graphite in the step (1) is 150um.
Further, the average particle diameter D50 of the resin powder in the step (2) is 15um;
the resin powder is polypropylene powder.
Further, the inert gas in the step (2) is argon.
Further, the temperature in the dispersing chamber of the gas flow disperser in the step (2) is controlled at 180 ℃.
Further, the pavement surface density in the step (3) is 1500g/m 2 。
Further, the thickness of the pre-pressing plate in the step (3) is 5mm.
Further, in the hot press molding step of step (4): pressing the pre-pressed plate into a hot pressing plate with the thickness of 1mm by a molding press, wherein:
the hot pressing temperature is 170 ℃, the pre-pressing time is 10min, and the pre-pressing pressure is 1MPa.
Further, in the cold press shaping step of step (5):
the hot-pressed plate was pressed into a bipolar plate with a thickness of 0.87mm by a die press at room temperature, wherein:
cold pressing time is 10min, cold pressing pressure is 25Mpa, and density of bipolar plate is 1.60g/cm 3 。
A flow battery bipolar plate is prepared by any one of the preparation methods.
The all-vanadium redox flow battery comprises the redox flow battery bipolar plate.
Example 4
A preparation method of a flow battery bipolar plate comprises the following specific steps:
(1) Expanding expandable graphite particles by a bulking furnace at high temperature to obtain graphite worms;
(2) Respectively mixing graphite worms and resin powder obtained in the step (1) according to a mass ratio of 85:15 blowing the mixture into an airflow disperser, and fully and uniformly mixing the mixture to obtain a mixture of resin and graphite worms;
(3) Mixing the resin obtained in the step (2) and graphite worms according to the surface density of 1500g/m 2 Filling to form cuboid spreading materials, and pre-pressing the spreading materials by a roll squeezer to obtain a pre-pressing plate;
(4) The pre-pressing plate is subjected to hot press molding through a roller press to obtain a hot pressing plate;
(5) And cold-pressing and shaping the hot pressing plate through a roller press to obtain the bipolar plate.
Further, the specific process parameters of the puffing treatment in the step (1) are as follows: the puffing temperature is 800 ℃, and the puffing time is 20s.
Further, the average particle diameter D50 of the expandable graphite in the step (1) is 150um.
Further, the average particle diameter D50 of the resin powder in the step (2) is 15um; the resin powder is polytetrafluoroethylene powder.
Further, the inert gas in the step (2) is helium.
Further, the temperature in the dispersing chamber of the gas flow disperser in the step (2) is controlled at 190 ℃.
Further, the pavement surface density in the step (3) is 1500g/m 2 。
Further, the thickness of the pre-pressing plate in the step (3) is 5mm.
Further, in the hot press molding step of step (4): pressing the pre-pressed plate into a hot pressing plate with the thickness of 1mm by a roller press, wherein:
the hot pressing temperature is 170 ℃, the pre-pressing time is 5min, and the pre-pressing pressure is 10MPa.
Further, in the cold press shaping step of step (5):
the hot-pressed plate was pressed into a bipolar plate with a thickness of 0.85mm by a roll press at room temperature, wherein:
cold pressing time is 8min, cold pressing pressure is 40Mpa, and density of bipolar plate is 1.63g/cm 3 。
A flow battery bipolar plate is prepared by any one of the preparation methods.
The all-vanadium redox flow battery comprises the redox flow battery bipolar plate.
Example 5
A preparation method of a flow battery bipolar plate comprises the following specific steps:
(1) Expanding expandable graphite particles by a bulking furnace at high temperature to obtain graphite worms;
(2) Respectively mixing graphite worms and resin powder obtained in the step (1) according to a mass ratio of 85:15 blowing the mixture into an airflow disperser, and fully and uniformly mixing the mixture to obtain a mixture of resin and graphite worms;
(3) Mixing the resin obtained in the step (2) and graphite worms according to the surface density of 1500g/m 2 Filling to form cuboid spreading materials, and pre-pressing the spreading materials by a molding press to obtain a pre-pressing plate;
(4) The pre-pressing plate is subjected to hot press molding through a molding press to obtain a hot pressing plate;
(5) And cold-pressing and shaping the hot pressing plate through a molding machine to obtain the bipolar plate.
In the step (2), the resin powder contacts with high-temperature graphite worms and is fused and adhered in the surface pores of the worms, so that a good mixing state of the resin and the graphite worms is ensured.
Further, the specific process parameters of the puffing treatment in the step (1) are as follows: the puffing temperature is 800 ℃, and the puffing time is 20s.
Further, the average particle diameter D50 of the expandable graphite of step (1) is 150m.
Further, the average particle diameter D50 of the resin powder in the step (2) is 15um;
the resin powder is polyethylene powder. In another embodiment, the resin powder is a mixture of polyvinylidene fluoride powder, polytetrafluoroethylene powder, polyethylene powder and polypropylene powder in equal mass ratio.
Further, the inert gas in the step (2) is neon. In another embodiment, the inert gas in the step (2) is a mixed gas of argon, helium and neon in equal volume ratio.
Further, the temperature in the dispersing chamber of the gas flow disperser in the step (2) is controlled at 190 ℃.
Further, the thickness of the pre-pressing plate in the step (3) is 5mm.
Further, in the hot press molding step of step (4): pressing the pre-pressed plate into a hot pressing plate with the thickness of 1mm by a molding press, wherein:
the hot pressing temperature is 170 ℃, the pre-pressing time is 5min, and the pre-pressing pressure is 15MPa.
Further, in the cold press shaping step of step (5):
the hot-pressed plate was pressed into a bipolar plate with a thickness of 0.86mm by a die press at room temperature, wherein:
cold pressing time is 8min, cold pressing pressure is 30Mpa, and density of bipolar plate is 1.64g/cm 3 。
A flow battery bipolar plate is prepared by any one of the preparation methods.
The all-vanadium redox flow battery comprises the redox flow battery bipolar plate.
Example 6
A preparation method of a flow battery bipolar plate comprises the following specific steps:
(1) Expanding expandable graphite particles by a bulking furnace at high temperature to obtain graphite worms;
(2) Respectively mixing graphite worms and resin powder obtained in the step (1) according to a mass ratio of 70:30 blowing the mixture into an airflow disperser, and fully and uniformly mixing the mixture to obtain a mixture of resin and graphite worms;
(3) Mixing the resin obtained in the step (2) and graphite worms according to the surface density of 1000g/m 2 Filling to form cuboid spreading materials, and pre-pressing the spreading materials by a molding press to obtain a pre-pressing plate;
(4) The pre-pressing plate is subjected to hot press molding through a molding press to obtain a hot pressing plate;
(5) And cold-pressing and shaping the hot pressing plate through a molding machine to obtain the bipolar plate.
Further, the specific process parameters of the puffing treatment in the step (1) are as follows: the puffing temperature is 600 ℃ and the puffing time is 50s.
Further, the average particle diameter D50 of the expandable graphite in the step (1) is 50um.
Further, the average particle diameter D50 of the resin powder in the step (2) is 1um;
the resin powder is polyvinylidene fluoride powder.
Further, the temperature in the dispersing chamber of the gas flow disperser in the step (2) is controlled at 150 ℃.
Further, the pavement surface density in the step (3) is 1000g/m 2 。
Further, the thickness of the pre-pressing plate in the step (3) is 1mm.
Further, in the hot press molding step of step (4): pressing the pre-pressed plate into a hot pressing plate with the thickness of 0.5mm by a molding press, wherein:
the hot pressing temperature is 120 ℃, the pre-pressing time is 10min, and the pre-pressing pressure is 30MPa.
Further, in the cold press shaping step of step (5):
the hot-pressed plate was pressed into a bipolar plate with a thickness of 0.3mm by a die press at room temperature, wherein:
cold pressing time is 1min, cold pressing pressure is 50Mpa, and density of bipolar plate is 1.4g/cm 3 。
A flow battery bipolar plate is prepared by any one of the preparation methods.
The all-vanadium redox flow battery comprises the redox flow battery bipolar plate.
Example 7
A preparation method of a flow battery bipolar plate comprises the following specific steps:
(1) Expanding expandable graphite particles by a bulking furnace at high temperature to obtain graphite worms;
(2) Respectively mixing graphite worms and resin powder obtained in the step (1) according to a mass ratio of 95:5, blowing the mixture into an airflow disperser, and fully and uniformly mixing the mixture to obtain a mixture of resin and graphite worms;
(3) Mixing the resin obtained in the step (2) and graphite worms according to the surface density of 2000g/m 2 Filling to form cuboid spreading materials, and pre-pressing the spreading materials by a molding press to obtain a pre-pressing plate;
(4) The pre-pressing plate is subjected to hot press molding through a molding press to obtain a hot pressing plate;
(5) And cold-pressing and shaping the hot pressing plate through a molding machine to obtain the bipolar plate.
Further, the specific process parameters of the puffing treatment in the step (1) are as follows: the puffing temperature is 1000 ℃ and the puffing time is 1s.
Further, the average particle diameter D50 of the expandable graphite in the step (1) is 300um.
Further, the average particle diameter D50 of the resin powder in the step (2) is 100um;
the resin powder is polytetrafluoroethylene powder.
Further, the inert gas in the step (2) is argon.
Further, the temperature in the dispersing chamber of the gas flow disperser in the step (2) is controlled at 250 ℃.
Further, the thickness of the pre-pressing plate in the step (3) is 10mm.
Further, in the hot press molding step of step (4): pressing the pre-pressed plate into a hot pressing plate with the thickness of 2mm by a die press, wherein:
the hot pressing temperature is 250 ℃, the pre-pressing time is 10min, and the pre-pressing pressure is 1MPa.
Further, in the cold press shaping step of step (5):
the hot-pressed plate was pressed into a bipolar plate having a thickness of 1.2mm by a die press at room temperature, wherein:
cold pressing time is 10min, and cold pressing pressure is 25Mpa. The density of the bipolar plate was 1.9g/cm 3 。
A flow battery bipolar plate is prepared by any one of the preparation methods.
The all-vanadium redox flow battery comprises the redox flow battery bipolar plate.
The embodiment discloses a preparation method of a flow battery bipolar plate, which comprises the following steps:
(1) Expanding graphite with the particle size of 150um at 800 ℃ for 20s to obtain graphite worms, and cooling for later use;
(2) Respectively blowing graphite worms and 20 mu m PVDF into an airflow mixer, wherein the mass ratio of the graphite worms to the PVDF is 85:15, obtaining the mixed material of PVDF and graphite worms.
(3) Mixing the materials according to the surface density of 1500g/cm 2 Spreading, and then pre-pressing by a roller press to prepare a pre-pressing plate with the thickness of 5 mm;
(4) Hot-press molding by a roller press, and pressing the pre-pressed plate into a hot-press plate with the thickness of 1mm, wherein the hot-press temperature is 170 ℃;
(5) Cold-pressing and shaping by a roll squeezer, and pressing the pre-pressed plate into a cold-pressed plate with the thickness of 0.83mm and the density of the bipolar plate of 1.65g/cm 3 。
The embodiment discloses a preparation method of a flow battery bipolar plate, which comprises the following steps:
(1) Expanding graphite with the particle size of 150um at 800 ℃ for 20s to obtain graphite worms, and cooling for later use;
(2) The graphite worms and 20um PVDF are blown into a gas flow mixer by nitrogen at 180 ℃, and the mass ratio of the worms to the PVDF is 85:15, obtaining the mixed material of PVDF and graphite worms.
(3) Mixing the materials according to the surface density of 1500g/cm 2 Spreading, and then pre-pressing by a roller press to prepare a pre-pressing plate with the thickness of 5 mm;
(4) Hot-press molding by a roller press, and pressing the pre-pressed plate into a hot-press plate with the thickness of 1mm, wherein the hot-press temperature is 170 ℃;
(5) Cold-pressing and shaping by a roll squeezer, and pressing the pre-pressed plate into a cold-pressed plate with the thickness of 0.83mm and the density of the bipolar plate of 1.63g/cm 3 。
As can be seen from the table above, the bipolar plate prepared by the method has higher conductivity and mechanical strength. It can be seen from examples 1, 2 and 3 that the graphite worms are increased in proportion, and the conductivity of the bipolar plate is greatly improved.
Comparing comparative example 1 and comparative example 2 with example 1, the bipolar plate prepared by the mixing process provided by the method of the invention has better conductive performance.
The embodiments of the present invention have been described in detail. However, the present invention is not limited to the above-described embodiments, and various modifications may be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (9)
1. The preparation method of the flow battery bipolar plate is characterized by comprising the following specific steps:
(1) Expanding expandable graphite particles by a bulking furnace at high temperature to obtain graphite worms;
(2) And (3) respectively mixing graphite worms obtained in the step (1) with resin powder according to the mass ratio of (70-95) by nitrogen or inert gas: (30-5) blowing into an airflow disperser, and fully and uniformly mixing to obtain a mixture of resin and graphite worms;
(3) Obtaining the product in the step (2)The obtained mixture of resin and graphite worm has the surface density of 1000-2000 g/m 2 Filling to form cuboid spreading materials, and pre-pressing the spreading materials by a roll squeezer or a die squeezer to obtain a pre-pressing plate;
(4) The pre-pressing plate is subjected to hot press molding through a roller press or a die press to obtain a hot pressing plate;
(5) And cold-pressing and shaping the hot pressing plate through a roller press or a die press to obtain the bipolar plate.
2. The method for preparing a bipolar plate of a flow battery according to claim 1, wherein the specific process parameters of the puffing treatment in the step (1) are as follows: puffing temperature of 600-1000 deg.C, puffing time of 1-50 s, and/or
The average particle diameter D50 of the expandable graphite in the step (1) is 50-300 um.
3. The method for producing a flow battery bipolar plate according to claim 1, wherein the average particle diameter D50 of the resin powder in the step (2) is 1 to 100 μm, and/or
The resin powder is one or more of polyvinylidene fluoride powder, polytetrafluoroethylene powder, polyethylene powder and polypropylene powder.
4. The method for preparing a bipolar plate of a flow battery according to claim 1, wherein the inert gas in the step (2) is one or more of argon, helium and neon, and/or
The temperature in the dispersing chamber of the air flow disperser in the step (2) is controlled to be 150-250 ℃.
5. The method for manufacturing a bipolar plate for a flow battery according to claim 1, wherein the thickness of the pre-pressing plate in the step (3) is 1-10 mm.
6. The method for manufacturing a bipolar plate for a flow battery according to claim 1, wherein in the hot press molding step of step (4): pressing the pre-pressed plate into a hot pressing plate with the thickness of 0.5-2 mm by a roller press or a die press, wherein:
the hot pressing temperature is 120-250 ℃, the pre-pressing time is 1-10 min, and the pre-pressing pressure is 1-30 MPa.
7. The method for preparing a bipolar plate of a flow battery according to claim 1, wherein in the cold press shaping process of step (5):
pressing the hot-pressed plate into a bipolar plate with the thickness of 0.3-1.2 mm at room temperature through a roller press or a die press, wherein:
cold pressing for 1-10 min at 25-50 MPa, and/or
The density of the bipolar plate is 1.4-1.9 g/cm 3 。
8. A flow battery bipolar plate prepared by the method of any one of claims 1-7.
9. An all-vanadium flow battery comprising the flow battery bipolar plate of claim 8.
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