CN116144092B - High-dimensional network structure bipolar plate for zinc-bromine flow battery and preparation method thereof - Google Patents
High-dimensional network structure bipolar plate for zinc-bromine flow battery and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 title claims abstract description 12
- -1 polyethylene Polymers 0.000 claims abstract description 54
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- 229920000573 polyethylene Polymers 0.000 claims abstract description 53
- 239000011231 conductive filler Substances 0.000 claims abstract description 45
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
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- 229920003023 plastic Polymers 0.000 claims abstract description 21
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- 239000003999 initiator Substances 0.000 claims abstract description 13
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- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 10
- 239000004917 carbon fiber Substances 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical group 0.000 claims description 3
- 150000001451 organic peroxides Chemical group 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229920001903 high density polyethylene Polymers 0.000 claims description 2
- 239000004700 high-density polyethylene Substances 0.000 claims description 2
- 229920001684 low density polyethylene Polymers 0.000 claims description 2
- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- 230000008961 swelling Effects 0.000 abstract description 16
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 4
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- 229920000642 polymer Polymers 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
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- 238000005520 cutting process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012745 toughening agent Substances 0.000 description 3
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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 application discloses a high-dimensional network structure bipolar plate for a zinc-bromine flow battery and a preparation method thereof. The preparation method comprises the following steps: s100, mixing conductive filler and a free radical initiator to obtain a conductive filler mixture; s200, mixing polyethylene particles with a reaction promoter to obtain a polyethylene mixture; s300, mixing, extruding and granulating the conductive filler mixture, the polyethylene mixture and the antioxidant to obtain conductive plastic master batches; and S400, melting and blending the conductive plastic master batch and polyethylene granules, extruding, calendaring and forming to obtain the bipolar plate. The bipolar plate provided by the application can effectively solve the problem of cracking between the bipolar plate and the electrode and between the bipolar plate and the carbon felt caused by swelling of the bipolar plate when the bipolar plate is in a liquid environment for a long time, ensures the stability of a flow battery, can effectively absorb impact energy when being impacted by outside due to the formation of a three-dimensional network structure, improves the toughness of the bipolar plate and solves the problem of difficult assembly of the bipolar plate.
Description
Technical Field
The application relates to the field of flow batteries, in particular to a high-dimensional network structure bipolar plate for a zinc-bromine flow battery and a preparation method thereof.
Background
At present, the consumption of fossil energy sources is increasingly remarkable, and the problems of environment and climate are caused, and accordingly renewable energy sources such as wind energy, solar energy, tidal energy and geothermal energy continuously enter the visual field of people, and electricity brought by the renewable energy sources is continuously absorbed by a national power grid, but the renewable energy sources have unstable power generation voltage, intermittent energy source supply and a plurality of uncontrollable factors, and an energy storage battery is needed to be equipped for solving the problems. The flow battery gradually becomes a research hot spot due to the advantages of low cost, good energy storage effect, safe use, low pollution and the like.
The bipolar plate is an important component of the flow battery, works in a liquid environment for a long time, and is easy to crack between the bipolar plate and an electrode and between the bipolar plate and a carbon felt due to swelling of polymer resin, so that the performance and the service life of the flow battery are affected. Carbon fibers and carbon nanotubes are commonly added into bipolar plates in industry to control the shrinkage rate of products and improve the conductivity of the bipolar plates, but the method has higher cost and can cause the problem of poor toughness of the bipolar plates.
The patent with publication number of CN108129747B discloses a preparation method of a composite bipolar plate, the problem of insufficient toughness of the bipolar plate is solved by adding a toughening agent, and data given by the preparation method obviously show that the conductivity of the bipolar plate is reduced along with the increase of the dosage of the toughening agent, and the bipolar plate is inevitably reduced in tensile strength due to the use of the toughening agent.
The patent with publication number CN112490460A discloses a preparation method of a composite bipolar plate, wherein the bipolar plate is injection molded by adding a carbon fiber component, so that the conductivity of the bipolar plate can be improved, but the carbon fiber component is added, so that stress concentration is generated at a carbon fiber when the bipolar plate material is stressed, and the toughness of the bipolar plate is reduced due to poor interfacial bonding capability between the surface inertia of the carbon fiber and a resin matrix; and the price of the carbon fiber is higher, and the production and manufacturing cost of the product is increased.
The application reduces the distribution area of conductive filler by foaming plastic, promotes the formation of conductive network structure in plastic particles and improves the conductivity. However, the application adds two working procedures of plastic particle physical foaming and extrusion and exhaust after plastic particle foaming, thus greatly increasing the difficulty and cost of industrial production.
Disclosure of Invention
The application aims to provide a high-dimensional network structure bipolar plate for a zinc-bromine flow battery, which has good mechanical property and swelling resistance.
The application further aims to provide a preparation method of the high-dimensional network structure bipolar plate for the zinc-bromine flow battery, which is low in cost and suitable for mass production.
In order to achieve the above purpose, the application provides a preparation method of a bipolar plate with a high-dimensional network structure for a zinc-bromine flow battery, which comprises the following steps:
s100, mixing conductive filler and a free radical initiator to obtain a conductive filler mixture;
s200, mixing polyethylene particles with a reaction promoter to obtain a polyethylene mixture;
s300, mixing, extruding and granulating the conductive filler mixture, the polyethylene mixture and the antioxidant to obtain conductive plastic master batches;
and S400, melting and blending the conductive plastic master batch and polyethylene granules, extruding, calendaring and forming to obtain the bipolar plate.
Further, the conductive filler is selected from one or more of graphite micropowder, conductive carbon black, carbon nanotubes, carbon fibers and graphene.
Further, the conductive filler is graphite micro powder, and the particle size of the conductive filler is 1-100 mu m.
Further, the free radical initiator is an organic peroxide.
Further, the reaction promoter is selected from metal oxides, sulfur, acrylate-based monomers, and allyl-based monomers.
Further, in step S100, the mass ratio of the conductive filler to the radical initiator is (10-20): 1.
Further, in step S200, the mass ratio of the polyethylene particles to the reaction accelerator is (10-30): 1.
Further, in step S300, the mass ratio of the conductive filler mixture to the polyethylene mixture is (1-2): 1.
Further, in step S400, the mass fraction of the conductive filler in the prepared bipolar plate is 30% -60%.
Further, the polyethylene particles are selected from one or more of low-density polyethylene, high-density polyethylene, linear polyethylene and grafted polyethylene, and the melt index of the polyethylene particles is 0.05-30.
Further, in step S300, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1098, antioxidant 1076, antioxidant 3114, and antioxidant 168.
Further, in both the step S100 and the step S200, a high-speed mixer is used for mixing, the rotation speed is 800-3000 r/min, and the mixing time is 1-20 min.
Further, in the step S300, the temperature of the extruder is 110-260 ℃ and the rotating speed of the extruder is 5-50 r/min.
Further, in step S400, the temperature of the extruder is 110-260 ℃, the rotating speed of the extruder is 5-50 r/min, and the temperature of the calendaring rollers is 80-260 ℃.
The application also provides a high-dimensional network structure bipolar plate for the zinc-bromine flow battery, which comprises polyethylene with a three-dimensional network structure and conductive filler dispersed in the polyethylene.
Further, the mass fraction of the conductive filler in the bipolar plate is 30% -60%, and the conductive filler is graphite micro powder with the particle size of 1-100 μm.
Compared with the prior art, the application has the beneficial effects that: the application adopts polyethylene as the base material for manufacturing the bipolar plate, which is beneficial to realizing continuous production and improving production efficiency; in addition, after the conductive filler and the polyethylene are respectively mixed with the free radical initiator and the reaction accelerator, the conductive plastic master batch with a three-dimensional network structure is obtained through melt extrusion, and the movement of a polymer molecular chain is blocked due to the formation of the three-dimensional network structure, the crystallinity of the polymer is reduced, and at the moment, the amorphous area in the polymer is increased, so that the distribution area of the conductive filler in the conductive plastic master batch is widened, and the dispersibility of the conductive filler in the conductive plastic master batch is improved; the bipolar plate can absorb external impact force better due to the formation of the three-dimensional network structure, the tensile strength and the impact strength of the bipolar plate are improved, and the problem of difficult assembly of the bipolar plate can be effectively solved; in addition, the formation of the three-dimensional network structure also enhances the binding between the internal molecular chains of the polymer, and water molecules enter the polymer under the water system environment of the flow battery, so that the macromolecule of the three-dimensional network structure becomes difficult to disassemble, the swelling of the polymer is reduced, the dimensional stability of a bipolar plate product is improved, the problem that the bipolar plate is broken between the bipolar plate, an electrode and a carbon felt due to the swelling of the bipolar plate when the bipolar plate is in a liquid environment for a long time is effectively solved, and the stability of the flow battery is ensured.
Drawings
FIG. 1 is an electron micrograph of the interior of a bipolar plate of example 1;
fig. 2 is a graph showing the bipolar plate constant current discharge test curves of the respective examples and comparative examples.
Detailed Description
The present application will be further described with reference to the following specific embodiments, and it should be noted that, on the premise of no conflict, new embodiments may be formed by any combination of the embodiments or technical features described below.
The terms "comprises" and "comprising," along with any variations thereof, in the description and claims, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The application provides a preparation method of a bipolar plate with a high-dimensional network structure for a zinc-bromine flow battery, which comprises the following steps:
s100, mixing conductive filler and a free radical initiator to obtain a conductive filler mixture;
s200, mixing polyethylene particles with a reaction promoter to obtain a polyethylene mixture;
s300, mixing, extruding and granulating the conductive filler mixture, the polyethylene mixture and the antioxidant to obtain conductive plastic master batches;
and S400, melting and blending the conductive plastic master batch and polyethylene granules, extruding, calendaring and forming to obtain the bipolar plate.
According to the application, the free radical initiator is matched with the reaction promoter, and a plurality of activation points are formed on the polyethylene molecular chain in the process of melting and extruding the conductive filler and the polyethylene, so that the polyethylene molecular chain is subjected to branching reaction, and the molecular chain is crosslinked and intertwined to initially form a star-shaped structure, and finally a three-dimensional net structure is formed in the polymer.
Due to the formation of the three-dimensional cross-linked structure, the movement of the polymer molecular chain is blocked, the crystallinity of the polymer is reduced, and at the moment, the amorphous area in the polymer is increased, so that the distribution area of the conductive filler in the conductive plastic master batch is widened, and the dispersibility of the conductive filler in the conductive plastic master batch is improved; according to the application, a three-dimensional network structure is spontaneously formed in the polymer, so that the constraint among molecular chains in the polymer is enhanced, water molecules enter the polymer in a flow battery water system environment, the macromolecule in the three-dimensional network structure is difficult to disassemble, the swelling of the polymer is reduced, and the dimensional stability of a bipolar plate product is improved; meanwhile, due to the formation of a three-dimensional network inside the bipolar plate, the bipolar plate can better absorb external impact force, and the tensile strength and the impact strength of the bipolar plate are improved.
Compared with the existing preparation technology of the composite bipolar plate, the preparation method has the advantages that the mechanical property and the swelling resistance of the bipolar plate are improved by adding the free radical initiator and the reaction accelerator, the stability of the bipolar plate in a liquid environment is guaranteed on the premise that the conductivity of the bipolar plate is not influenced, and therefore the long-term stability of the flow battery is improved.
It should be noted that the radical reaction of polyethylene mainly occurs in step S300, and of course, in step S400, there is also a certain radical reaction, so as to further form a three-dimensional network structure.
It will be appreciated by those skilled in the art that the polyethylene particles of the present application are non-crosslinked polyethylene, i.e., the polyethylene particles have not yet been crosslinked to form a three-dimensional network.
Further, the conductive filler is selected from one or more of graphite micropowder, conductive carbon black, carbon nanotubes, carbon fibers and graphene. The cost of the graphite micropowder is lower than that of the carbon nano tube and the carbon fiber, and the conductivity of the graphite micropowder is better than that of the conductive carbon black in a highly aggregated state, so the conductive filler of the application is preferably the graphite micropowder, and the particle size of the graphite micropowder is 1-100 mu m.
Further, the free radical initiator is an organic peroxide, which may be, but is not limited to, dicumyl Peroxide (DPC), di-t-butyl peroxide (DTBP), benzoyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate.
The reaction promoter may be, but is not limited to, metal oxides (e.g., zinc oxide, magnesium oxide, etc.), sulfur, acrylate-based promoters, allyl-based promoters.
The antioxidants in step S300 may be, but are not limited to, antioxidant 1010, antioxidant 1098, antioxidant 1076, antioxidant 3114, antioxidant 168.
Further, in both the step S100 and the step S200, a high-speed mixer is used for mixing, the rotation speed is 800-3000 r/min, and the mixing time is 1-20 min.
In the step S300, the temperature of the extruder is 110-260 ℃, and the rotating speed of the extruder is 5-50 r/min. In the step S400, the temperature of the extruder is 110-260 ℃, the rotating speed of the extruder is 5-50 r/min, and the temperature of the calendaring rollers is 80-260 ℃.
The application also provides a bipolar plate for the flow battery, and the base material of the bipolar plate comprises polyethylene with a three-dimensional network structure and conductive filler dispersed in the polyethylene.
[ example 1 ]
(1) Adding 300g of graphite micropowder and 20g of DPC into a high-speed mixer, and mixing for 10min at the rotating speed of 800r/min to obtain a conductive filler mixture after full mixing;
(2) Adding 300g of polyethylene particles and 10g of zinc oxide into a high-speed mixer, and mixing for 15min at the rotating speed of 800r/min to obtain a polyethylene mixture after full mixing;
(3) Mixing the conductive filler mixture in the step (1), the polyethylene mixture in the step (2) and 5g of antioxidant by a high-speed mixer at a rotating speed of 1200r/min for 30min, fully adding the mixture into an extruder for melting and granulating to prepare conductive plastic master batches, wherein the temperature of the extruder is set to be 200 ℃, and the rotating speed of the extruder is set to be 30r/min;
(4) And (3) melt blending the conductive plastic master batch obtained in the step (3) with 400g of polyethylene granules, extruding, calendaring and forming to obtain the bipolar plate, wherein the temperature of the extruder is 200 ℃, the rotating speed of the extruder is 30r/min, and the temperature of the calendaring roller is 110 ℃.
[ example 2 ]
Example 2 is different from example 1 in that the amount of graphite fine powder added in step (1) is 400g, the amount of antioxidant added in step (3) is 10g, and the amount of polyethylene particles added in step (4) is 300g.
[ example 3 ]
Example 3 is different from example 1 in that the amount of fine graphite powder added in step (1) was 500g, the amount of antioxidant added in step (3) was 10g, and the amount of polyethylene particles added in step (4) was 200g.
[ example 4 ]
Example 4 differs from example 1 in that the amount of graphite fine powder added in step (1) was 600g, the amount of antioxidant added in step (3) was 10g, and the amount of polyethylene particles added in step (4) was 100g.
Comparative example 1
(1) Fully and uniformly mixing 300g of conductive filler and 300g of polyethylene in a high-speed mixer, wherein the rotating speed of the high-speed mixer is 1200r/min, and the time is 30min;
(2) And (3) adding the mixture obtained in the step (1) into an extruder for melting and granulating to prepare conductive plastic master batch, wherein the temperature of the extruder is set to be 200 ℃, and the rotating speed of the extruder is set to be 30r/min.
(3) And (3) melt blending the conductive plastic master batch obtained in the step (2) with 400g of polyethylene granules, extruding, calendaring and forming to obtain the bipolar plate, wherein the temperature of the extruder is 200 ℃, the rotating speed of the extruder is 30r/min, and the temperature of the calendaring roller is 110 ℃.
The tensile strength, bending strength, electrical conductivity and swelling degree of the bipolar plates prepared in each example and comparative example were measured, and the experimental results are recorded in table 1. It is worth mentioning that the swelling degree test method comprises the following steps: cutting the prepared bipolar plate into 10cm sample plates by using a high-speed digital cutting system, ensuring that the surface of the bipolar plate is not damaged when the digital cutting system cuts the bipolar plate, keeping the bipolar plate intact, and measuring and recording the mass M of the sample plates at the moment 1 The method comprises the steps of carrying out a first treatment on the surface of the Placing a bipolar plate template into the electrolyte of the zinc-bromine flow battery, fixing four corners of the template, keeping the electrolyte at a constant temperature, and soaking for two weeks, wherein the set constant temperature range is 60-90 ℃; taking out the bipolar plate template, placing the bipolar plate template in a vacuum drying oven, drying, cooling and weighing to obtain the mass M of the bipolar plate 2 The temperature of the drying oven is 100-200 ℃, and the drying time is 10-30 min; calculate bipolar plate swelling (%) =m 2 /M 1 。
TABLE 1
| Tensile Strength (MPa) | Flexural Strength (MPa) | Conductivity (S/cm) | Swelling degree (%) | |
| Example 1 | 25.7 | 48 | 7 | 115 |
| Example 2 | 23.1 | 45 | 9 | 121 |
| Example 3 | 21.4 | 38 | 12 | 112 |
| Example 4 | 18.2 | 26 | 15 | 103 |
| Comparative example 1 | 23.4 | 40 | 6 | 150 |
As can be seen from the data in table 1, as the content of the conductive filler increases, the conductivity is continuously improved, but the mechanical properties of the bipolar plate are continuously reduced, and the brittleness is continuously improved, so that the assembly of the galvanic pile is affected. Comparative example 1 has the same content of conductive filler as example 1 (both 30%), but the tensile strength, flexural strength and electrical conductivity of the bipolar plate of example 1 are all superior to those of comparative example 1, and the swelling degree of example 1 is significantly smaller than that of comparative example 1. The mechanical properties of the bipolar plate of example 2 are not much different from those of comparative example 1, but the content of the conductive filler (40%) in example 2 is greater than that of comparative example 1 (30%), which indicates that the formation of a three-dimensional network structure can increase the content of the conductive filler while ensuring that the mechanical properties are not degraded. In addition, the swelling degree of example 2 is increased compared with that of example 1 because the increase in the content of the conductive filler makes the bonding between the filler and the matrix worse and the limitation of the filler on the polyethylene molecular chain worse. The reason why the swelling degree of examples 3 and 4 is lower than that of example 1 is that the swelling of the bipolar plate is mainly caused by the polymer in examples 3 and 4 due to the decrease in the polymer content, and thus the swelling ratio is also lowered when the polymer content is decreased to some extent.
Fig. 1 is an electron microscopic view of the bipolar plate of example 1, in which graphite fine powder is dispersed between network-like molecular chains.
Fig. 2 is a graph of the bipolar plate constant current discharge test of examples 1 to 4 and comparative example 1, which is shown as example 4, example 3, example 2, example 1 and comparative example 1 in order from top to bottom.
The foregoing has outlined the basic principles, features, and advantages of the present application. It will be understood by those skilled in the art that the present application is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present application, and various changes and modifications may be made therein without departing from the spirit and scope of the application, which is defined by the appended claims. The scope of the application is defined by the appended claims and equivalents thereof.
Claims (7)
1. The preparation method of the bipolar plate with the high-dimensional network structure for the zinc-bromine flow battery is characterized by comprising the following steps of:
s100, mixing conductive filler and free radical initiator to obtain conductive filler mixture, wherein the mass ratio of the conductive filler to the free radical initiator is (10-20): 1;
s200, mixing polyethylene particles and a reaction promoter to obtain a polyethylene mixture, wherein the mass ratio of the polyethylene particles to the reaction promoter is (10-30) 1;
s300, mixing the conductive filler mixture, the polyethylene mixture and the antioxidant, extruding and granulating to obtain conductive plastic master batches, wherein in the melt extrusion process, polyethylene is crosslinked under the action of a free radical initiator and a reaction promoter, and the mass ratio of the conductive filler mixture to the polyethylene mixture is (1-2): 1;
s400, melting and blending the conductive plastic master batch and polyethylene granules, extruding, calendaring and forming to obtain the bipolar plate, wherein the mass fraction of the conductive filler in the bipolar plate is 30% -60%.
2. The method of claim 1, wherein the conductive filler is selected from one or more of graphite micropowder, conductive carbon black, carbon nanotubes, carbon fibers, and graphene.
3. The method according to claim 2, wherein the conductive filler is graphite fine powder having a particle diameter of 1 to 100 μm.
4. The method of claim 1, wherein the free radical initiator is an organic peroxide and the reaction promoter is selected from the group consisting of metal oxides, sulfur, acrylate-based promoters, and allyl-based promoters.
5. The method of claim 1, wherein the polyethylene particles are selected from the group consisting of low density polyethylene, high density polyethylene, linear polyethylene, and a blend of one or more of grafted polyethylene, and the polyethylene particles have a melt index of 0.05 to 30.
6. The preparation method of claim 1, wherein in step S100 and step S200, a high-speed mixer is used for mixing at a rotation speed of 800-3000 r/min for 1-20 min;
in the step S300, the temperature of the extruder is 110-260 ℃ and the rotating speed of the extruder is 5-50 r/min;
in the step S400, the temperature of the extruder is 110-260 ℃, the rotating speed of the extruder is 5-50 r/min, and the temperature of the calendaring rollers is 80-260 ℃.
7. A high-dimensional network bipolar plate for a zinc-bromine flow battery prepared by the method of any one of claims 1 to 6, comprising a polyethylene having a three-dimensional network structure and a conductive filler dispersed in the polyethylene.
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