CN114805715A - Novel phenolic resin and application thereof in preparation of flexible graphite-based bipolar plate - Google Patents
Novel phenolic resin and application thereof in preparation of flexible graphite-based bipolar plate Download PDFInfo
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- CN114805715A CN114805715A CN202210472379.0A CN202210472379A CN114805715A CN 114805715 A CN114805715 A CN 114805715A CN 202210472379 A CN202210472379 A CN 202210472379A CN 114805715 A CN114805715 A CN 114805715A
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- bipolar plate
- graphite
- phenolic resin
- flexible graphite
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 147
- 239000010439 graphite Substances 0.000 title claims abstract description 147
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 66
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 6
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000003377 acid catalyst Substances 0.000 claims abstract description 3
- 230000009471 action Effects 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- ZAZOCQFBLVVZPT-UHFFFAOYSA-N 5-[2-methyl-5-(trifluoromethyl)pyrazol-3-yl]thiophene-2-carbaldehyde Chemical compound CN1N=C(C(F)(F)F)C=C1C1=CC=C(C=O)S1 ZAZOCQFBLVVZPT-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000004327 boric acid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 229910021382 natural graphite Inorganic materials 0.000 claims description 10
- 238000005452 bending Methods 0.000 claims description 8
- -1 phenolic aldehyde Chemical class 0.000 claims description 7
- 239000000446 fuel Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 3
- 238000009830 intercalation Methods 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 claims description 2
- NAVUFVFBPAZJJT-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)benzaldehyde Chemical compound O=CC1=CC=CC(OCC2OC2)=C1 NAVUFVFBPAZJJT-UHFFFAOYSA-N 0.000 claims 1
- 230000002687 intercalation Effects 0.000 claims 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract description 10
- 238000012545 processing Methods 0.000 abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 5
- 239000005977 Ethylene Substances 0.000 abstract description 5
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000005096 rolling process Methods 0.000 description 11
- 239000003085 diluting agent Substances 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 230000035699 permeability Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 235000006408 oxalic acid Nutrition 0.000 description 6
- 239000008399 tap water Substances 0.000 description 6
- 235000020679 tap water Nutrition 0.000 description 6
- 239000004246 zinc acetate Substances 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- RIBSTTPRQPAXRS-UHFFFAOYSA-N (5-formylfuran-3-yl)boronic acid Chemical compound OB(O)C1=COC(C=O)=C1 RIBSTTPRQPAXRS-UHFFFAOYSA-N 0.000 description 4
- RHAXKFFKGZJUOE-UHFFFAOYSA-N 7-acetyl-6-ethyl-3,5,8-trihydroxy-9,10-dioxoanthracene-1,2-dicarboxylic acid Chemical compound O=C1C2=CC(O)=C(C(O)=O)C(C(O)=O)=C2C(=O)C2=C1C(O)=C(CC)C(C(C)=O)=C2O RHAXKFFKGZJUOE-UHFFFAOYSA-N 0.000 description 4
- 229930192967 Laccaic acid Natural products 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 description 1
- WWSJZGAPAVMETJ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethoxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OCC WWSJZGAPAVMETJ-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000004497 pyrazol-5-yl group Chemical group N1N=CC=C1* 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
-
- 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
- H01M8/0213—Gas-impermeable carbon-containing materials
-
- 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
- H01M8/0221—Organic resins; Organic polymers
-
- 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
- H01M8/0226—Composites in the form of mixtures
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Energy (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses novel phenolic resin and application thereof in preparation of flexible graphite-based bipolar plates, and relates to the technical field of processing and manufacturing of bipolar plates. The preparation method of the novel phenolic resin comprises the following steps: mixing the raw materials, and generating novel phenolic resin through polycondensation under the action of an acid catalyst; wherein the raw material components at least comprise phenol and 3- (ethylene oxide-2-yl methoxyl) benzaldehyde. The novel phenolic resin prepared by the invention is applied to the preparation of the bipolar plate, the mechanical property of the bipolar plate is obviously improved, the electric conductivity of the bipolar plate can be obviously enhanced, and the air tightness and the acid and alkali resistance are better.
Description
Technical Field
The invention belongs to the technical field of bipolar plate processing and manufacturing, and particularly relates to novel phenolic resin and application thereof in preparation of flexible graphite-based bipolar plates.
Background
Bipolar plates are key components in Proton Exchange Membrane Fuel Cells (PEMFCs), where they function to distribute fuel gas and air, to achieve electrical coupling between individual cells, to carry away waste heat from the active area, to prevent leakage of gas and coolant, and to facilitate water management in the cell. In recent years, polymer/flexible graphite materials have become a suitable fuel cell bipolar plate material due to their low cost, high electrical conductivity, high flexibility, and ease of processing. In the prior art, two main methods for preparing the bipolar plate by using the flexible graphite plate as the raw material exist. One is to form a flow field plate by one-step molding of a low-density flexible graphite plate, then carry out resin impregnation, and finally carry out curing molding. This process is used, for example, in the patent WO0041260 by Ballard corporation which teaches polyvinylidene fluoride/flexible graphite bipolar plates. The bipolar plate prepared by the method is easy to form, but the resin impregnation effect is not ideal, and the gas permeability and the mechanical property of the material are influenced. It can be seen that if a low-cost, lightweight, and excellent bipolar plate material can be selected, the bipolar plate and thus the entire fuel cell system will be greatly advanced and well-padded for their industrialization.
Disclosure of Invention
The invention aims to provide novel phenolic resin and application thereof in preparation of flexible graphite-based bipolar plates, wherein the novel phenolic resin is applied to preparation of the bipolar plates, so that the mechanical property of the bipolar plates is obviously improved, the electric conductivity of the bipolar plates can be obviously enhanced, and the air tightness and the acid and alkali resistance are better.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a preparation method of a novel phenolic resin comprises the following steps: mixing the raw materials, and generating novel phenolic resin through polycondensation under the action of an acid catalyst;
wherein the raw material components at least comprise phenol and 3- (ethylene oxide-2-yl methoxyl) benzaldehyde.
Preferably, the starting components also comprise 2- [ 1-methyl-3- (trifluoromethyl) pyrazol-5-yl ] thiophene-5-carbaldehyde and/or 5-formylfuran-3-boronic acid. The invention adopts 2- [ 1-methyl-3- (trifluoromethyl) pyrazol-5-yl ] thiophene-5-formaldehyde and/or 5-aldehyde furan-3-boric acid as a polycondensation monomer, and prepares the novel phenolic resin by compounding with other components. The flexible graphite-based bipolar plate is applied to the preparation of flexible graphite-based bipolar plate materials, the mechanical property of the bipolar plate is obviously improved by utilizing the performance of the resin material, and the bending strength of the bipolar plate is obviously improved; the novel phenolic resin prepared by the invention can effectively improve the conductivity of the bipolar plate while ensuring excellent mechanical properties, and the conductivity is effectively improved; and the novel phenolic resin is cured at high temperature to form a more compact network structure, so that the gas tightness of the bipolar plate material is obviously enhanced, and the gas permeability is obviously reduced. In addition, the bipolar plate material containing the novel phenolic resin prepared by the method is also remarkably enhanced in corrosion resistance and has more excellent acid resistance and alkali resistance.
Preferably, the molar ratio of the phenolic aldehyde in the raw materials is 1.2-1.4: 1.
specifically, the preparation method of the novel phenolic resin comprises the following steps:
heating phenol to 65-70 ℃, sequentially adding deionized water, 3- (ethylene oxide-2-ylmethoxy) benzaldehyde, 2- [ 1-methyl-3- (trifluoromethyl) pyrazol-5-yl ] thiophene-5-formaldehyde and 5-aldehyde furan-3-boric acid, mixing, adding zinc acetate and oxalic acid, adjusting the pH to be less than 2.5, reacting for 1-3 hours at 90-100 ℃, and carrying out reduced pressure distillation to obtain novel phenolic resin;
or the like, or, alternatively,
heating phenol to 65-70 ℃, sequentially adding deionized water, 3- (ethylene oxide-2-ylmethoxy) benzaldehyde and 2- [ 1-methyl-3- (trifluoromethyl) pyrazol-5-yl ] thiophene-5-formaldehyde, mixing, adding zinc acetate and oxalic acid, adjusting the pH to be less than 2.5, reacting for 1-3 hours at 90-100 ℃, and carrying out reduced pressure distillation to obtain a novel phenolic resin;
or the like, or, alternatively,
heating phenol to 65-70 ℃, sequentially adding deionized water, 3- (ethylene oxide-2-methoxy) benzaldehyde and 5-aldehyde furan-3-boric acid, mixing, adding zinc acetate and oxalic acid, adjusting the pH to be less than 2.5, reacting for 1-3 h at 90-100 ℃, and carrying out reduced pressure distillation to obtain the novel phenolic resin.
Preferably, the solid-to-liquid ratio of the phenol to the deionized water is 0.6-0.8 g/mL; the molar ratio of 3- (oxiranyl-2-ylmethoxy) benzaldehyde, 2- [ 1-methyl-3- (trifluoromethyl) pyrazol-5-yl ] thiophene-5-carbaldehyde and 5-formylfuran-3-boronic acid is 1: 0.3-0.5: 0.2 to 0.4; the molar ratio of the zinc acetate to the phenol is 0.03-0.05: 1; the adding amount of the oxalic acid is 0.3-0.5 wt% of the phenol.
The invention also discloses application of the novel phenolic resin prepared by the preparation method in preparation of flexible graphite-based bipolar plates.
A preparation method of a flexible graphite-based bipolar plate comprises the following steps: the bipolar plate is formed by filling graphite pores into a reinforced resin vacuum environment and pressing at high temperature by using flexible natural graphite as a base material;
wherein the reinforcing resin comprises one of phenolic resin and epoxy resin; the phenolic resin comprises the novel phenolic resin prepared by the preparation method. The bipolar plate provided by the invention is prepared by filling graphite pores into a reinforced resin in a vacuum environment and pressing at high temperature by taking flexible natural graphite as a base material, and is simple in preparation process and convenient for batch production; the low-density flexible graphite plate is pre-pressed, so that the resin content in the bipolar plate is easily controlled and adjusted, and the thickness of the bipolar plate is reduced. The novel phenolic resin impregnated graphite base plate prepared by the method has the advantages that the mechanical property of the obtained bipolar plate material is better, the electric conduction capability is obviously improved, the bipolar plate material has more excellent corrosion resistance, the gas tightness of the bipolar plate is higher, and the novel phenolic resin impregnated graphite base plate material is beneficial to promoting the industrialized development of fuel cells.
Specifically, the preparation method of the flexible graphite-based bipolar plate comprises the following steps:
preparing flexible graphite paper:
the graphite worms are pressed into graphite sponge cake plates in multiple sections, and then pressed into graphite sponge cake plates with the density of more than or equal to 1.0g/cm by multiple rolling presses 3 The flexible graphite paper of (2);
preparing a bipolar plate:
soaking flexible graphite paper in 15-40 wt% resin diluent under the condition of vacuum negative pressure of 0.1-0.3 MPa, and maintaining the pressure for 6-8 h; taking out the surface to wipe, pressurizing and drying the solvent, and then pressurizing and curing at high temperature to obtain the flexible graphite-based bipolar plate.
Preferably, the length of the graphite worms is 0.6-1.2 cm.
Preferably, the graphite worms are prepared by intercalating natural graphite with a strong acid to prepare acidified particles and expanding the acidified particles at high temperatures.
Specifically, the preparation method of the graphite worms comprises the following steps:
taking 280-300 parts by weight of 98% sulfuric acid, adding 3-5 parts by weight of 55-60% hydrogen peroxide aqueous solution, cooling to 8-10 ℃, adding scaly natural graphite with the granularity of 30-80 meshes, reacting for 20-50 min, then performing suction filtration and deionized water cleaning, repeating the operation for 2-3 times, and drying at 100-110 ℃ to obtain expandable graphite; and (3) processing the graphite for 2-8 seconds at the high temperature of 950-1100 ℃ to form vermicular graphite, and separating gas from gas to obtain graphite worms.
Preferably, the density of the graphite sponge cake board is 0.1-0.2 g/cm 3 。
Preferably, the pressure applied in the multi-pass rolling step is 85-110 Mpa, the temperature is 180-250 ℃, and the rolling speed is 3-4 m/min.
Preferably, in the preparation step of the bipolar plate, the diluent is selected from one of common tap water, IMBK and 20-30 wt% ethanol water solution; the temperature of the drying solvent is 80-90 ℃; the high-temperature curing temperature is 120-140 ℃.
More preferably, the modified expanded graphite is obtained by modifying the graphite worms in the preparation process of the flexible graphite paper, and the specific operations comprise:
mixing graphite worms and laccaic acid, performing vortex oscillation and uniform mixing, performing melt mixing under the condition of a water bath at 100-110 ℃, and standing for 4-6 hours to obtain the modified expanded graphite. According to the invention, the graphite worms and the laccaic acid are mixed by a melt blending method to obtain the modified expanded graphite, and the modified expanded graphite is pressed into the graphite paper and then compounded with the resin to obtain the flexible graphite-based bipolar plate, so that the mechanical property of the bipolar plate is further improved, the conductivity of the bipolar plate is improved, and the gas tightness of the bipolar plate can be effectively enhanced.
Preferably, the resin content in the flexible graphite-based bipolar plate is 14-25 wt%.
The invention also aims to provide the flexible graphite-based bipolar plate prepared by the preparation method.
Preferably, the mass ratio of the graphite worms to the eleostearic acid is 1: 4 to 6.
Preferably, the bending strength of the bipolar plate is more than 20MPa, and the electric conductivity is more than 150 s/cm; more preferably, the bipolar plate has a flexural strength of > 35MPa and an electrical conductivity of > 183 s/cm.
The invention also discloses the application of the flexible graphite-based bipolar plate in the preparation of a proton exchange membrane fuel cell.
Compared with the prior art, the invention has the following beneficial effects:
the flexible graphite-based bipolar plate is obtained by filling graphite pores into a reinforced resin vacuum environment and pressing at high temperature by using flexible natural graphite as a base material. The novel phenolic resin prepared by the method obviously improves the mechanical property of the bipolar plate, effectively improves the conductivity of the bipolar plate, and has higher gas tightness and obviously enhanced corrosion resistance. In addition, the graphite worms and the laccaic acid are mixed by adopting a melt blending method to obtain modified expanded graphite, the modified expanded graphite is pressed into graphite paper and then compounded with resin to obtain the flexible graphite-based bipolar plate, the mechanical property of the bipolar plate is further improved, the conductivity of the bipolar plate is improved, and meanwhile, the gas tightness of the bipolar plate can be effectively enhanced.
Therefore, the invention provides the novel phenolic resin and the application thereof in preparing the flexible graphite-based bipolar plate, the novel phenolic resin is applied to the preparation of the bipolar plate, the mechanical property of the bipolar plate is obviously improved, the electric conductivity of the bipolar plate can be obviously enhanced, and the air tightness and the acid and alkali resistance are better.
Drawings
FIG. 1 shows the IR spectrum test results of the novel phenol resin in test example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1:
preparing a flexible graphite-based bipolar plate:
preparing flexible graphite paper:
adding 295 parts by weight of 98% sulfuric acid, 5 parts by weight of 60% aqueous hydrogen peroxide, cooling to 10 ℃, adding scaly natural graphite with the particle size distribution of 30-80 meshes, reacting for 40min, performing suction filtration and deionized water cleaning, repeating the operation for 3 times, and drying at 110 ℃ to obtain expandable graphite; processing the graphite for 8s at the high temperature of 1000 ℃ and expanding the graphite into vermicular graphite, and separating the vermicular graphite from gas and materials to obtain graphite worms with the length of 0.6-1.2 cm;
then evenly paving the graphite worms, and rolling to obtain the graphite worms with the density of 0.1g/cm 3 The graphite sponge cake board of (1); then, carrying out multi-pass rolling pressing to obtain flexible graphite paper, wherein the pressure applied in the rolling step is 100Mpa, the temperature is 230 ℃, and the rolling speed is 4 m/min; the density of the obtained flexible graphite paper is 1.0g/cm 3 ；
Preparing a bipolar plate:
placing flexible graphite paper into a vacuum tank body, keeping the negative pressure at 0.1MPa, and introducing 25 wt% of phenolic resin diluent which is common tap water; maintaining the pressure of the vacuum tank for 6 hours; then taking out the flexible graphite paper filled with the phenolic resin in the pores, and wiping residual resin on the surface; pressurizing and drying solvent water in the graphite paper at the temperature of 80 ℃, and then pressurizing and curing resin in the graphite paper at the temperature of 130 ℃ to obtain a flexible graphite-based bipolar plate; the resin content in the obtained flexible graphite-based bipolar plate was 19.4 wt%.
Example 2:
preparing a flexible graphite-based bipolar plate:
the flexible graphite paper was prepared differently from example 1: the density of the prepared flexible graphite paper is 1.6g/cm 3 ；
The bipolar plate was prepared differently from example 1: the pressure maintaining time of the vacuum tank is 8 h.
The resin content in the flexible graphite-based bipolar plate was 23.6 wt%.
Example 3:
preparing a flexible graphite-based bipolar plate:
the flexible graphite paper was prepared differently from example 1: making flexible graphite paperThe density was 1.5g/cm 3 ；
Preparing a bipolar plate:
placing flexible graphite paper into a vacuum tank body, keeping the negative pressure at 0.1MPa, and introducing 25 wt% of phenolic resin diluent which is common tap water; maintaining the pressure of the vacuum tank for 6 hours and introducing 6kg of compressed air; then taking out the flexible graphite paper filled with the phenolic resin in the pores, and wiping residual resin on the surface; and (3) drying solvent water in the graphite paper under the condition of 80 ℃ under the pressure, and then curing resin in the graphite paper under the condition of 130 ℃ under the pressure to obtain the flexible graphite-based bipolar plate.
The resin content in the flexible graphite-based bipolar plate was 22.1 wt%.
Example 4:
preparing a flexible graphite-based bipolar plate:
the flexible graphite paper was prepared as in example 3;
the bipolar plate was prepared differently from example 3: replacing phenolic resin diluent with epoxy resin diluent, and replacing common tap water with IMBK; meanwhile, the pressure maintaining time of the vacuum tank is 8 hours.
The resin content in the flexible graphite-based bipolar plate was 23.0 wt%.
Example 5:
preparing a flexible graphite-based bipolar plate:
the flexible graphite paper was prepared as in example 1;
the bipolar plate was prepared differently from example 1: epoxy resin diluent is adopted to replace phenolic resin diluent, and IMBK is adopted to replace common tap water.
The resin content in the flexible graphite-based bipolar plate was 20.2 wt%.
Example 6:
preparing novel phenolic resin:
heating phenol to 70 ℃, sequentially adding deionized water, 3- (ethylene oxide-2-ylmethoxy) benzaldehyde, 2- [ 1-methyl-3- (trifluoromethyl) pyrazol-5-yl ] thiophene-5-formaldehyde and 5-aldehyde furan-3-boric acid to mix (the phenolic molar ratio is 1.3: 1), adding zinc acetate and oxalic acid, adjusting the pH value to 2.0, reacting for 2 hours at 100 ℃, and carrying out reduced pressure distillation to obtain the novel phenolic resin.
In the preparation process, the solid-to-liquid ratio of phenol to deionized water is 0.75 g/mL; the molar ratio of 3- (oxiranyl-2-ylmethoxy) benzaldehyde, 2- [ 1-methyl-3- (trifluoromethyl) pyrazol-5-yl ] thiophene-5-carbaldehyde and 5-formylfuran-3-boronic acid is 1: 0.4: 0.3; the molar ratio of zinc acetate to phenol was 0.04: 1; the amount of oxalic acid added was 0.42 wt% of phenol.
Preparing a flexible graphite-based bipolar plate:
the flexible graphite paper was prepared as in example 1;
the bipolar plate was prepared differently from example 1: the novel phenolic resin diluent prepared in the embodiment is used for replacing a phenolic resin diluent, and an ethanol solution with the concentration of 25% is used for replacing common tap water.
Example 7:
the preparation of the novel phenolic resin differs from example 6 in that: the molar ratio of the phenolic aldehyde is 1.2: 1; the molar ratio of 3- (oxiranyl-2-ylmethoxy) benzaldehyde, 2- [ 1-methyl-3- (trifluoromethyl) pyrazol-5-yl ] thiophene-5-carbaldehyde and 5-formylfuran-3-boronic acid is 1: 0.46: 0.23.
preparing a flexible graphite-based bipolar plate:
the flexible graphite paper was prepared as in example 1;
the bipolar plate was prepared differently from example 1: the novel phenolic resin was prepared in this example.
Example 8:
the preparation of the novel phenolic resin differs from example 6 in that: 3- (ethylene oxide-2-methoxyl) benzaldehyde is adopted to replace 5-aldehyde furan-3-boric acid.
Preparing a flexible graphite-based bipolar plate:
the flexible graphite paper was prepared as in example 6;
the bipolar plate was prepared differently from example 6: the novel phenolic resin was prepared in this example.
Example 9:
the preparation of the novel phenolic resin differs from example 6 in that: 3- (oxiranyl-2-methoxyl) benzaldehyde is adopted to replace 2- [ 1-methyl-3- (trifluoromethyl) pyrazol-5-yl ] thiophene-5-formaldehyde.
Preparing a flexible graphite-based bipolar plate:
the flexible graphite paper was prepared as in example 6;
the bipolar plate was prepared differently from example 6: the novel phenolic resin was prepared in this example.
Example 10:
the preparation of the novel phenolic resin differs from example 6 in that: 3- (oxiranyl-2-yl methoxyl) benzaldehyde is adopted to replace 2- [ 1-methyl-3- (trifluoromethyl) pyrazol-5-yl ] thiophene-5-formaldehyde and 5-aldehyde furan-3-boric acid.
Preparing a flexible graphite-based bipolar plate:
the flexible graphite paper was prepared as in example 6;
the bipolar plate was prepared differently from example 6: the novel phenolic resin was prepared in this example.
Example 11:
the preparation of the novel phenolic resin was the same as in example 6.
Preparing a flexible graphite-based bipolar plate:
preparing flexible graphite paper:
adding 295 parts by weight of 98% sulfuric acid, 5 parts by weight of 60% aqueous hydrogen peroxide, cooling to 10 ℃, adding scaly natural graphite with the particle size distribution of 30-80 meshes, reacting for 40min, performing suction filtration and deionized water cleaning, repeating the operation for 3 times, and drying at 110 ℃ to obtain expandable graphite; processing the graphite for 8s at the high temperature of 1000 ℃ and expanding the graphite into vermicular graphite, and separating the vermicular graphite from gas and materials to obtain graphite worms with the length of 0.6-1.2 cm;
according to the mass ratio of 1: 5.2, mixing the graphite worms and the laccaic acid according to the proportion, uniformly mixing by vortex oscillation, placing the mixture in a water bath condition at 105 ℃ for melting and mixing, and standing for 5.5 hours to obtain modified expanded graphite;
uniformly paving the modified expanded graphite, and rolling to obtain the product with density of 0.1g/cm 3 The graphite sponge cake board of (1); then, a plurality of rolling presses are carried out to obtain flexible graphite paper, wherein the pressure applied in the rolling stepThe force is 100Mpa, the temperature is 230 ℃, and the rolling speed is 4 m/min; the density of the obtained flexible graphite paper is 1.0g/cm 3 ；
The bipolar plate was prepared differently from example 6: flexible graphite paper was prepared for this example.
Example 12:
preparing a flexible graphite-based bipolar plate:
the flexible graphite paper was prepared differently from example 1: the flexible graphite paper was prepared as in example 11.
The bipolar plate was prepared differently from example 1: flexible graphite paper was prepared for this example.
Example 13:
the preparation of the novel phenolic resin was the same as in example 10.
Preparing a flexible graphite-based bipolar plate:
the flexible graphite paper was prepared differently from example 10: the flexible graphite paper was prepared as in example 11.
The bipolar plate was prepared differently from example 10: flexible graphite paper was prepared for this example.
Test example 1:
1. FT-IR characterization
And testing the sample by using a Fourier infrared transform spectrometer. And (3) placing the sample under an attenuated total reflection accessory, and scanning the surface of the sample to obtain an infrared spectrogram. The test conditions are specifically as follows: the scanning wavelength is 500-4000 cm -1 。
The above tests were carried out on the novel phenolic resins prepared in example 6 and example 10, the results of which are shown in figure 1. From the analysis in the figure, the infrared spectrum of the novel phenolic resin prepared in example 1 is 1688cm, which is compared with the infrared test result of the novel phenolic resin prepared in example 10 -1 A characteristic absorption peak of 1655cm, in which C is equal to C bond, appears nearby -1 A characteristic absorption peak of C ═ N bonds appears nearby, and the absorption peak is 1326cm -1 A characteristic absorption peak of C-N bond appears nearby; at 1090cm -1 A characteristic absorption peak of C-F bond appears nearby; at 982cm -1 A characteristic absorption peak of C-S bond appears nearby; the above results show that 2- [ 1-methyl-3- (trifluoro-1-methyl)Methyl) pyrazol-5-yl]Thiophene-5-formaldehyde successfully participates in the polycondensation reaction; at 1370cm -1 A characteristic absorption peak of a B-O bond appears nearby, which shows that the novel phenolic resin structure comprises 5-aldehyde furan-3-boric acid; the above results show the successful preparation of the novel phenolic resin in example 6.
Test example 2:
bipolar plate performance testing
1. Measurement of bending Strength
The test was carried out by three-point bending, the sample was processed to a size of 5X 60mm, and ground with sandpaper to grind the four corners of the sample into circular arcs. And (3) testing conditions are as follows: the loading speed was 5 mm/min. The bending strength (σ) was calculated according to the following formula:
σ＝3P 0 L/(2bh 2 )
in the formula, P 0 Represents the load, N; l represents span, mm; h represents the height at the port, mm; b denotes the width, mm.
2. Determination of the conductivity
The test method is carried out according to the standard specified by YB/T120-97. The test uses a double-arm bridge, and the resistivity is calculated according to the following formula:
ρ＝RS/l
in the formula, ρ represents resistivity, Ω · m; r represents resistance, Ω; s represents the cross-sectional area of the sample, m 2 (ii) a l represents the distance between two lines in the middle of the sample, m.
3. Gas permeability determination
The test method is carried out according to the standards specified in ASTM D1434, GB 1038 and ISO 2556. The specific operation comprises the following steps: hydrogen and inert gas with the temperature of (25 +/-2) DEG C and the pressure of 0.1MPa are respectively introduced into the two sides of the clamp gas chamber, so that the pressure of the two sides of the gas chamber is kept balanced. After stabilization for 6h under these conditions, the inert gas outlet was passed through a gas chromatograph to measure the concentration. And calculated according to the following formula:
C＝q/S
wherein C represents the hydrogen transmission rate per unit time and unit area, cm, of the bipolar plate 3 /cm 2 S; q represents a gas permeation amount per unit time, cm 3 S; s represents penetrationEffective test area of the cell, cm 2 。
The results of the three tests on the flexible graphite-based bipolar plates prepared in examples 1 to 13 are shown in table 1:
table 1 bipolar plate performance test results
| Sample (I) | Flexural Strength (MPa) | Conductivity (s/cm) | Transmittance (. times.10) -6 cm 3 /cm 2 ·s) |
| Example 1 | 20.4 | 154 | 4.08 |
| Example 2 | 22.1 | 158 | 3.84 |
| Example 3 | 20.7 | 153 | 3.96 |
| Example 4 | 21.5 | 157 | 3.89 |
| Example 5 | 20.9 | 156 | 3.95 |
| Example 6 | 35.2 | 183 | 2.04 |
| Example 7 | 36.1 | 185 | 1.98 |
| Example 8 | 23.4 | 170 | 3.09 |
| Example 9 | 23.0 | 167 | 2.92 |
| Example 10 | 22.6 | 160 | 3.94 |
| Example 11 | 40.9 | 197 | 1.21 |
| Example 12 | 26.3 | 164 | 3.17 |
| Example 13 | 28.7 | 169 | 3.10 |
From the analysis in table 1, it can be seen that the flexible graphite-based bipolar plates prepared in examples 1 to 5 have excellent bending strength and conductivity and relatively low gas permeability, which indicates that the bipolar plates prepared by the invention have good mechanical properties, excellent conductivity and good air tightness. The electrical conductivity of the flexible graphite-based bipolar plate prepared in example 8 and example 9 is better than that of example 10, the gas permeability is lower than that of example 10, and the bending strength is equivalent to that of example 10, which shows that the novel phenolic resin prepared by using 2- [ 1-methyl-3- (trifluoromethyl) pyrazol-5-yl ] thiophene-5-formaldehyde or 5-aldehyde furan-3-boric acid as one of the condensation monomers can effectively improve the electrical conductivity and the air tightness of the bipolar plate and does not have negative influence on the mechanical property of the bipolar plate when being applied to the preparation of the bipolar plate. The bending strength and the electric conductivity of the flexible graphite-based bipolar plate prepared in example 6 are better than those of examples 8-9, and the gas permeability is lower than those of examples 8-9, which shows that the novel phenolic resin prepared by using 2- [ 1-methyl-3- (trifluoromethyl) pyrazol-5-yl ] thiophene-5-formaldehyde and 5-aldehyde furan-3-boric acid as condensation monomers is applied to preparation of the bipolar plate, so that the mechanical property of the bipolar plate can be remarkably enhanced, and the synergistic effect is better in the improvement effect of the electric conductivity and the air tightness of the bipolar plate.
In addition, the flexural strength and the electrical conductivity of the flexible graphite-based bipolar plate prepared in example 11 are better than those of example 6, the gas permeability is lower than those of example 6, the effect of example 12 is better than that of example 1, and the effect of example 13 is better than that of example 10, which shows that the novel phenolic resin prepared by using 2- [ 1-methyl-3- (trifluoromethyl) pyrazol-5-yl ] thiophene-5-formaldehyde and 5-aldehyde furan-3-boric acid as condensation monomers is applied to the preparation of the bipolar plate, so that the mechanical property of the bipolar plate can be remarkably improved, the electrical conductivity of the bipolar plate is improved, and the air tightness of the bipolar plate is improved.
4. Test of Corrosion resistance
Weighing the pretreated sample with the same mass, then respectively adding the pretreated sample into 50% hydrochloric acid solution and 20% sodium hydroxide solution for soaking corrosion, and sealing the preservative film. After 10 days, the sample was removed and dried in a vacuum oven at 80 ℃ for 1h to substantially evaporate the surface water and determine its mass. The corrosion resistance of the bipolar plate is characterized by the sample mass loss rate before and after soaking.
The results of the above tests on the flexible graphite-based bipolar plates prepared in examples 1 and 6 to 13 are shown in table 2:
table 2 corrosion resistance test results
As can be seen from the data in table 2, the mass loss rate of the flexible graphite-based bipolar plates prepared in examples 8 and 9 after being soaked in acid-base solution is significantly lower than that of example 10, which indicates that the novel phenolic resin prepared by using 2- [ 1-methyl-3- (trifluoromethyl) pyrazol-5-yl ] thiophene-5-formaldehyde or 5-aldehyde furan-3-boric acid as one of the condensation monomers is applied to preparation of the bipolar plates, and the corrosion resistance of the bipolar plates can be effectively improved. The mass loss rate of the flexible graphite-based bipolar plate prepared in the example 6 after being soaked in the acid-base solution is obviously lower than that of the flexible graphite-based bipolar plate prepared in the examples 8-9, and the gas permeability is lower than that of the flexible graphite-based bipolar plate prepared in the examples 8-9, which indicates that the novel phenolic resin prepared by using 2- [ 1-methyl-3- (trifluoromethyl) pyrazol-5-yl ] thiophene-5-formaldehyde and 5-aldehyde furan-3-boric acid as condensation monomers is applied to the preparation of the bipolar plate, and the synergistic effect has a better effect on improving the corrosion resistance of the bipolar plate.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A preparation method of a novel phenolic resin comprises the following steps: mixing the raw materials, and generating novel phenolic resin through polycondensation under the action of an acid catalyst;
wherein the raw material components at least comprise phenol and 3- (oxirane-2-yl methoxyl) benzaldehyde.
2. The method for preparing a novel phenolic resin according to claim 1, characterized in that: the raw material components also comprise 2- [ 1-methyl-3- (trifluoromethyl) pyrazol-5-yl ] thiophene-5-formaldehyde and/or 5-aldehyde furan-3-boric acid.
3. The method for preparing a novel phenolic resin according to claim 1, characterized in that: the molar ratio of the phenolic aldehyde in the raw materials is 1.2-1.4: 1.
4. use of the novel phenolic resin prepared by the preparation method of any one of claims 1 to 3 in preparation of flexible graphite-based bipolar plates.
5. A preparation method of a flexible graphite-based bipolar plate comprises the following steps: the bipolar plate is formed by filling graphite pores into a reinforced resin vacuum environment and pressing at high temperature by using flexible natural graphite as a base material;
the reinforcing resin comprises one of phenolic resin and epoxy resin; the phenolic resin comprises the novel phenolic resin prepared by the preparation method of any one of claims 1 to 3.
6. The method of claim 5, wherein the step of forming the flexible graphite-based bipolar plate comprises: the flexible natural graphite comprises graphite worms, and the length of the graphite worms is 0.6-1.2 cm.
7. The method of claim 6, wherein the step of forming the flexible graphite-based bipolar plate comprises: the graphite worms are prepared by preparing acidified particles from natural graphite through strong acid intercalation and expanding at high temperature.
8. A flexible graphite-based bipolar plate produced by the production method according to claim 5.
9. The flexible graphite-based bipolar plate of claim 8, wherein: the bending strength of the bipolar plate is more than 20MPa, and the electric conductivity of the bipolar plate is more than 150 s/cm.
10. Use of the flexible graphite-based bipolar plate of claim 8 in the manufacture of a proton exchange membrane fuel cell.
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| CN117207561A (en) * | 2023-11-07 | 2023-12-12 | 寰泰储能科技股份有限公司 | Bipolar plate for all-vanadium redox flow battery and preparation method thereof |
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| CN101447571A (en) * | 2008-12-29 | 2009-06-03 | 新源动力股份有限公司 | Preparation method of flexible graphite composite bipolar plate of proton exchange membrane fuel cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101447571A (en) * | 2008-12-29 | 2009-06-03 | 新源动力股份有限公司 | Preparation method of flexible graphite composite bipolar plate of proton exchange membrane fuel cell |
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| 郑水林等: "《非金属矿加工技术与应用手册》", 冶金工业出版社, pages: 602 - 603 * |
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| CN117207561A (en) * | 2023-11-07 | 2023-12-12 | 寰泰储能科技股份有限公司 | Bipolar plate for all-vanadium redox flow battery and preparation method thereof |
| CN117207561B (en) * | 2023-11-07 | 2024-02-23 | 寰泰储能科技股份有限公司 | Bipolar plate for all-vanadium redox flow battery and preparation method thereof |
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