CN102780020B - A kind of preparation method of fuel cell composite proton exchange membrane - Google Patents
A kind of preparation method of fuel cell composite proton exchange membrane Download PDFInfo
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- CN102780020B CN102780020B CN201210274802.2A CN201210274802A CN102780020B CN 102780020 B CN102780020 B CN 102780020B CN 201210274802 A CN201210274802 A CN 201210274802A CN 102780020 B CN102780020 B CN 102780020B
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- Prior art keywords
- parts
- sulfonated polyether
- polyether sulphone
- triethoxysilicane
- styrol copolymer
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- Expired - Fee Related
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- 239000000446 fuel Substances 0.000 title claims abstract description 13
- 239000012528 membrane Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002131 composite material Substances 0.000 title claims abstract description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 28
- 229920000570 polyether Polymers 0.000 claims abstract description 28
- 125000001174 sulfone group Chemical group 0.000 claims abstract description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920001577 copolymer Polymers 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- IBRQUKZZBXZOBA-UHFFFAOYSA-N 1-chloro-3-(3-chlorophenyl)sulfonylbenzene Chemical compound ClC1=CC=CC(S(=O)(=O)C=2C=C(Cl)C=CC=2)=C1 IBRQUKZZBXZOBA-UHFFFAOYSA-N 0.000 claims abstract description 5
- CWMYWRMDANXCSB-UHFFFAOYSA-N 1-oxoethanesulfonic acid Chemical compound CC(=O)S(O)(=O)=O CWMYWRMDANXCSB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 206010039424 Salivary hypersecretion Diseases 0.000 claims abstract description 5
- 208000008630 Sialorrhea Diseases 0.000 claims abstract description 5
- 230000006837 decompression Effects 0.000 claims abstract description 5
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- KDFGCKXYSYXQTO-UHFFFAOYSA-N phenol 1,2,3,4-tetramethyl-5-phenylbenzene Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.CC=1C(=C(C(=C(C1)C1=CC=CC=C1)C)C)C KDFGCKXYSYXQTO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 239000011347 resin Substances 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 238000007790 scraping Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 abstract 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- 239000005062 Polybutadiene Substances 0.000 abstract 1
- 229920002857 polybutadiene Polymers 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 241000255964 Pieridae Species 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 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
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- Polyethers (AREA)
Abstract
The invention discloses the preparation method of a kind of fuel cell composite proton exchange membrane, comprise the steps: tetramethyl biphenyl diphenol monomer, dichloro diphenyl sulfone and 3, in 3 ' sodium disulfonates at room temperature mixed organic solvents, under an inert atmosphere, reaction sucking filtration obtain sulfonated polyether sulphone；Sulfonated polyether sulphone is dissolved in polypyrrole, is subsequently adding diisocyanate resin, heats up, and continues reaction hour, be cooled to room temperature after adding triethoxysilicane styrene, and precipitation, sucking filtration obtains sulfonated polyether sulphone block triethoxysilicane styrol copolymer；Sulfonated polyether sulphone block triethoxysilicane styrol copolymer is dissolved in methylformamide and stirs; then the acetyl sulfonate of part is dripped; decompression is distilled off dimethylformamide; sucking filtration obtains sulfonated polyether sulphone block triethoxysilicane styrol copolymer sol gel solution; stirring sol gel solution makes it freely volatilize; solution sialorrhea after volatilization is on polyfluortetraethylene plate, and aeration-drying obtains sulfonated polyether sulphone block sulfonated polybutadiene proton exchange film.
Description
Technical field
The present invention relates to the preparation method of a kind of fuel cell composite proton exchange membrane, particularly relating to one can make
The preparation method of the PEM of standby high conductivity, non-oxidizability and alcohol-rejecting ability.
Background technology
In recent years, through the effort of various countries scientist Yu related industry personnel, fuel cell critical material be
System integrated technology obtains and develops rapidly, and supporting industry also reaches its maturity.Proton Exchange Membrane Fuel Cells
(PEMFC) use solid electrolyte polymeric membrane as electrolyte, therefore there is energy transformation ratio high and low temperature
The advantages such as startup, the leakage of electroless pond, corrosion-free, life-span length.Therefore it is acknowledged as most promising to be boat
My god, military, electric automobile and the first-selected power supply in regional power station.PEM is as pem fuel
The critical component of battery, it plays a part to isolate fuel and oxidant and proton conducting, and its performance is certainly
Determine the performance of fuel cell.Therefore improve PEM various aspects of performance, apparatus is answered for fuel cell
Significant.
Summary of the invention
It is an object of the invention to provide the preparation method of the fuel cell composite proton exchange membrane of a kind of excellent performance,
This compound proton exchange membrane can provide higher conductivity, non-oxidizability and alcohol-rejecting ability.
To achieve these goals, the preparation method of a kind of fuel cell composite proton exchange membrane that the present invention provides
Comprise the steps:
Step 1, in terms of mass parts: by 3～7 parts of tetramethyl biphenyl diphenol monomers, the dichloro diphenyl sulfone of 4～8 parts,
With 2～5 part 3,3 '-sodium disulfonate is at room temperature dissolved in the mixed organic solvents of 30～80 parts, at indifferent gas
Under atmosphere, it is warming up to 170 DEG C～180 DEG C, reacts 20～25 hours, after reaction terminates, product is cooled down
To room temperature, after sucking filtration, filtrate is poured in 150～250 parts of alcohol, quickly stir, generate precipitation, filter
To sulfonated polyether sulphone；
Step 2, in terms of mass parts: be dissolved in 30～200 parts of polypyrroles by 3-8 part sulfonated polyether sulphone, so
Rear addition 0.03～0.06 part of diisocyanate resin, be warming up to 100 DEG C, reacts 3～10 hours, adds 2 parts
Continue reaction 20～25 hours after triethoxysilicane styrene, be cooled to room temperature, pour 200-500 part methanol into
Or ethanol precipitates, it is filtrated to get sulfonated polyether sulphone block triethoxysilicane styrol copolymer；
Step 3, in terms of mass parts: by molten for 1 part of sulfonated polyether sulphone block triethoxysilicane styrol copolymer
In 20～30 parts of dimethylformamides and stir, the then acetyl sulfonate of dropping 0.5～10 part,
Reacting 10～20 hours at 70 DEG C～90 DEG C, after reaction terminates, decompression is distilled off dimethylformamide, then
Solution is poured in methanol or the ethanol of 100～200 parts, with the NaOH of 10～15 parts of 25wt% weight concentrations
Solution regulation pH value to 7～8, be filtrated to get sulfonated polyether sulphone block triethoxysilicane styrol copolymer
Sol-gel solution；
Step 4, shifts sulfonated polyether sulphone block triethoxysilicane styrol copolymer sol-gel solution
In culture dish, under magnetic stirring, sol-gel solution freely volatilizees, and the solution sialorrhea after volatilization is in poly-
On tetrafluoroethene plate, aeration-drying 1.5 days under room epidemic disaster is 50% environment, then the speed with 5 DEG C/h
From room temperature to 105 DEG C, and it is incubated 2.5h at 105 DEG C, after scraping, i.e. obtains PEM.
Preferably, the alcohol in step 1 is methanol or ethanol.
The ion exchange capacity of PEM prepared by the present invention is big, electrical conductivity is high, antioxidation and alcohol-rejecting ability
It is remarkably improved.
Detailed description of the invention
Embodiment one
In terms of mass parts: by 3 parts of tetramethyl biphenyl diphenol monomers, the dichloro diphenyl sulfone of 4 parts and 2 part 3,3 '-
Sodium disulfonate is at room temperature dissolved in the mixed organic solvents of 30 parts, in an inert atmosphere, is warming up to
170 DEG C, react 20 hours, after reaction terminates, product is cooled to room temperature, after sucking filtration, by filtrate
Pouring in 150 parts of ethanol, quickly stir, generate precipitation, sucking filtration obtains sulfonated polyether sulphone；By 3 parts of sulphurs
Change polyether sulphone to be dissolved in 30 parts of polypyrroles, be subsequently adding 0.03 part of diisocyanate resin, be warming up to 100 DEG C,
React 3 hours, continue reaction 20 hours after adding 2 parts of triethoxysilicane styrene, be cooled to room temperature,
Pouring in 200 parts of methanol or ethanol and precipitate, sucking filtration obtains sulfonated polyether sulphone block triethoxysilicane styrene
Copolymer；1 part of sulfonated polyether sulphone block triethoxysilicane styrol copolymer is dissolved in 20 parts of dimethyl
In Methanamide and stir, the then acetyl sulfonate of dropping 1 part, reacts 10 hours, instead at 70 DEG C
After should terminating, decompression is distilled off dimethylformamide, and then solution poured into methanol or the ethanol of 100 parts
In, with the solution regulation pH value of the NaOH of 10 parts of 25wt% weight concentrations to 7～8, sucking filtration obtains sulfonation
Polyaryl ether sulfone block triethoxysilicane styrol copolymer sol-gel solution；Sulfonated polyether sulphone block three second
Epoxide silicon styrol copolymer sol-gel solution is transferred in culture dish, under magnetic stirring, and sol-gel
Solution freely volatilizees, and the solution sialorrhea after volatilization, on polyfluortetraethylene plate, is 50% ring at room epidemic disaster
Aeration-drying 1.5 days under border, then with the speed of 5 DEG C/h from room temperature to 105 DEG C, and 105 DEG C of insulations
2.5h, i.e. obtains PEM with scalpel after scraping.
After tested, the ion exchange capacity of the PEM thus prepared is 0.73mmol/g, and electrical conductivity is
0.151S/cm (90 DEG C, 100%R.H.), non-oxidizability and alcohol-rejecting ability are remarkably improved.
Embodiment two
In terms of mass parts: by 7 parts of tetramethyl biphenyl diphenol monomers, the dichloro diphenyl sulfone of 8 parts and 5 part 3,3 '-
Sodium disulfonate is at room temperature dissolved in the mixed organic solvents of 30～80 parts, under an inert atmosphere, is warming up to
180 DEG C, react 25 hours, after reaction terminates, product is cooled to room temperature, after sucking filtration, by filtrate
Pouring in 250 parts of methanol, quickly stir, generate precipitation, sucking filtration obtains sulfonated polyether sulphone；By 8 parts of sulphurs
Change polyether sulphone to be dissolved in 200 parts of polypyrroles, be subsequently adding 0.06 part of diisocyanate resin, be warming up to
100 DEG C, react 10 hours, after adding 2 parts of triethoxysilicane styrene, continue reaction 25 hours, cooling
To room temperature, pouring in 500 parts of methanol or ethanol and precipitate, sucking filtration obtains sulfonated polyether sulphone block triethoxy
Silicon styrol copolymer；1 part of sulfonated polyether sulphone block triethoxysilicane styrol copolymer is dissolved in 30
In part dimethylformamide and stir, the then acetyl sulfonate of dropping 7 parts, reacts 20 at 90 DEG C
Hour, after reaction terminates, decompression is distilled off dimethylformamide, and then solution poured into the first of 200 parts
In alcohol or ethanol, regulate pP value H to 7-8 with the solution of the NaOH of 15 parts of 25wt% weight concentrations, take out
Filter obtains sulfonated polyether sulphone block triethoxysilicane styrol copolymer sol-gel solution；Sulfonated polyether
Sulfone block triethoxysilicane styrol copolymer sol-gel solution is transferred in culture dish, under magnetic stirring,
Sol-gel solution freely volatilizees, and the solution sialorrhea after volatilization is on polyfluortetraethylene plate, at room epidemic disaster
It is aeration-drying 1.5 days under 50% environment, then with the speed of 5 DEG C/h from room temperature to 105 DEG C, and
105 DEG C of insulation 2.5h, i.e. obtain PEM with scalpel after scraping.
After tested, the ion exchange capacity of the PEM thus prepared is 0.75mmol/g, and electrical conductivity is
0.143S/cm (90 DEG C, 100%R.H.), non-oxidizability and alcohol-rejecting ability are remarkably improved.
The above, be only presently preferred embodiments of the present invention, and the present invention not does any pro forma limit
System, although the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any familiar
Professional and technical personnel, without departing from technical scheme, when in the technology of available the disclosure above
Hold and make a little change or be modified to the Equivalent embodiments of equivalent variations, as long as being without departing from technical solution of the present invention
Content, any simple modification above example made according to the technical spirit of the present invention, equivalent variations with
Modify, all still fall within the range of technical solution of the present invention.
Claims (2)
1. the preparation method of a fuel cell composite proton exchange membrane, it is characterised in that comprise the steps:
Step 1, in terms of mass parts: by 3～7 parts of tetramethyl biphenyl diphenol monomers, the dichloro diphenyl sulfone of 4～8 parts and 2～5 part 3,3 '-sodium disulfonate is at room temperature dissolved in the mixed organic solvents of 30～80 parts, under an inert atmosphere, it is warming up to 170 DEG C～180 DEG C, reacts 20～25 hours, after reaction terminates, product is cooled to room temperature, after sucking filtration, filtrate is poured in 150～250 parts of alcohol, quickly stir, generate precipitation, be filtrated to get sulfonated polyether sulphone；
Step 2, in terms of mass parts: 3-8 part sulfonated polyether sulphone is dissolved in 30～200 parts of polypyrroles, it is subsequently adding 0.03～0.06 part of diisocyanate resin, it is warming up to 100 DEG C, react 3～10 hours, continue reaction 20～25 hours after adding 2 parts of triethoxysilicane styrene, be cooled to room temperature, pour in 200-500 part methanol or ethanol and precipitate, be filtrated to get sulfonated polyether sulphone block triethoxysilicane styrol copolymer；
Step 3, in terms of mass parts: 1 part of sulfonated polyether sulphone block triethoxysilicane styrol copolymer is dissolved in 20～30 parts of dimethylformamides and stirs, then the acetyl sulfonate of dropping 0.5～10 part, react 10～20 hours at 70 DEG C～90 DEG C, after reaction terminates, decompression is distilled off dimethylformamide, then solution is poured in methanol or the ethanol of 100～200 parts, pH value is regulated to 7～8 with the solution of the NaOH of 10～15 parts of 25wt% weight concentrations, it is filtrated to get sulfonated polyether sulphone block triethoxysilicane styrol copolymer sol-gel solution；
Step 4, sulfonated polyether sulphone block triethoxysilicane styrol copolymer sol-gel solution is transferred in culture dish, under magnetic stirring, sol-gel solution freely volatilizees, solution sialorrhea after volatilization on polyfluortetraethylene plate, aeration-drying 1.5 days under room epidemic disaster is 50% environment, then with the speed of 5 DEG C/h from room temperature to 105 DEG C, and it is incubated 2.5h at 105 DEG C, i.e. obtain PEM after scraping.
Method the most according to claim 1, it is characterised in that the alcohol in step 1 is methanol or ethanol.
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| CN201210274802.2A CN102780020B (en) | 2012-08-03 | 2012-08-03 | A kind of preparation method of fuel cell composite proton exchange membrane |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113207A (en) * | 2007-06-27 | 2008-01-30 | 中国科学技术大学 | Sol-gel ultraviolet/heat cross-linking preparation method of hybridized anion exchange membrane |
| CN101775202A (en) * | 2010-02-05 | 2010-07-14 | 山东天维膜技术有限公司 | Method based on sulfonated polyphenylene oxide for preparing organic-inorganic hybrid cation-exchange membranes |
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- 2012-08-03 CN CN201210274802.2A patent/CN102780020B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113207A (en) * | 2007-06-27 | 2008-01-30 | 中国科学技术大学 | Sol-gel ultraviolet/heat cross-linking preparation method of hybridized anion exchange membrane |
| CN101775202A (en) * | 2010-02-05 | 2010-07-14 | 山东天维膜技术有限公司 | Method based on sulfonated polyphenylene oxide for preparing organic-inorganic hybrid cation-exchange membranes |
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