CN101771159B - Proton exchange membrane and preparation method thereof - Google Patents
Proton exchange membrane and preparation method thereof Download PDFInfo
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- CN101771159B CN101771159B CN201010104002A CN201010104002A CN101771159B CN 101771159 B CN101771159 B CN 101771159B CN 201010104002 A CN201010104002 A CN 201010104002A CN 201010104002 A CN201010104002 A CN 201010104002A CN 101771159 B CN101771159 B CN 101771159B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000012528 membrane Substances 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 52
- 239000004696 Poly ether ether ketone Substances 0.000 claims abstract description 30
- 229920002530 polyetherether ketone Polymers 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000004695 Polyether sulfone Substances 0.000 claims description 27
- 229920006393 polyether sulfone Polymers 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 229920000557 Nafion® Polymers 0.000 description 20
- 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 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 150000003460 sulfonic acids Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000002079 cooperative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920004695 VICTREX™ PEEK Polymers 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003457 sulfones Chemical group 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 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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- Fuel Cell (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention provides a proton exchange membrane with excellent proton conductivity, high mechanical strength, high stability and low cost and a preparation method thereof. The proton exchange membrane is prepared from a blend of sulfonated polyether ether ketone with more than 60 percent and less than 100 percent of sulfonation degree and SPES with more than 0 percent and less than 60 percent of sulfonation degree, wherein the the proportion of sulfonated polyether ether ketone in the blend is between 30 and 50 weight percent; and the proportion of SPES in the blend is between 50 and 70 weight percent.
Description
Technical field
The present invention relates to a kind of PEM and preparation method thereof.
Background technology
Perfluorinated sulfonic acid type PEM is present widely used commodity PEM, and wherein the most representative is Nafion
series membranes that U.S. DuPont company produces.Perfluorinated sulfonic acid type PEM has good, proton conductivity advantages of higher when water content is high of mechanical strength height, chemical stability, is widely used in Proton Exchange Membrane Fuel Cells, PEM brine electrolysis and ion-exchange membrane electrolyzer system caustic soda.
Yet also there is following deficiency in perfluorinated sulfonic acid type PEM: at first, complex manufacturing, valuable product are like Nafion
The price of series membranes is up to 500～800$/m
2Secondly, the proton conductivity of perfluorinated sulfonic acid type PEM depends on water content in the film strongly, and under lower or temperature is higher (＞80 ℃) the anhydrous again additional situation, proton conductivity can significantly descend in water content; Once more, Nafion
The methanol crossover phenomenon was serious when film was applied to DMFC (DMFC); And methanol crossover will cause waste of fuel, reduce film conductivity, cathod catalyst poisoned and reduce cathode efficiency, above-mentioned shortcoming has seriously limited the application and the occasion of perfluorinated sulfonic acid type PEM.
In order to overcome the shortcoming of perfluorinated sulfonic acid type PEM; Various in recent years non-fluosulfonic acid type proton exchange polymer membranes occur in succession; Wherein polyether-ether-ketone (PEEK) has high temperature resistant, character such as chemical stability good, mechanical strength height, is insoluble in any strong acid, highly basic and the organic solvent except the concentrated sulfuric acid.Carry out sulfonation after polyether-ether-ketone dissolved and to make sulfonated polyether-ether-ketone (SPEEK) in the concentrated sulfuric acid or oleum; Because the SPEEK preparation method is simple, reaction condition is gentle, sulfonation degree can be regulated through the control reaction condition, filming performance is good; And the methanol permeability of SPEEK film is lower than Nafion
film, had Many researchers that SPEEK is processed non-fluosulfonic acid type PEM and be applied to hydrogen oxygen fuel cell and DMFC in.
The proton conductivity height of SPEEK film is mainly by its sulfonation degree and the moistening degree decision of film.When sulfonation degree was 60～90%, the membranous sub-conductivity of SPEEK was higher, but mechanical strength, thermal stability and the dimensional stability of film under moisture state significantly reduces, even possibly in hot water, dissolve.Thereby highly sulfonated SPEEK film (sulfonation degree＞60%) does not have practicality.
Another kind of important non-fluorine proton exchange membrane material is through the synthetic sulfonated polyether sulfone (SPES) of polycondensation reaction.The sulfonated polyether sulfone film has proton conductivity height, mechanical strength height, thermal stability and good chemical stability.
The researchers of Virginia, US Polytechnics [M.Sankir, V.A.Bhanu, W.L.Harrison etc., J.Appl.Polym.Sci., 2006,100,4595～4602; F.Wang, M.Hickner, Y.S.Kim etc., J.Membr.Sci., 2002,197:231～242] with dichloro diphenyl sulfone (DCDPS), sulfonation dichloro diphenyl sulfone (SDCDPS) and bisphenol-A copolymerization, obtain a kind of novel sulfonated polyether sulfone membrane material PBPSH.Through changing the ratio of SDCDPS and DCDPS, can obtain the PEM of different sulfonation degree values.Under 30 ℃, when SDCDPS/DCDPS ratio was 0.4, the conductivity of film was 0.11Scm
-1SDCDPS/DCDPS ratio is 0.6 o'clock, and the conductivity of film can reach 0.17Scm
-1, and Nafion under the same terms
The conductivity of 1135 films is merely 0.12Scm
-1In addition, the methanol permeability of PBPSH film is lower than Nafion
117 films.In the time of 80 ℃, the PBPSH film is at H
2Battery performance and Nafion among/airPEMFC and the DMFC
The battery performance of 117 films is suitable, and in the time of 60 ℃, the DMFC performance of PBPSH film is superior to Nafion
The battery performance of 117 films.
Though the membranous sub-conductivity of PBPSH sulfonated polyether sulfone is high, film forming is relatively poor, is easy to generate the embrittlement phenomenon.And owing to contain two sulfonic acid groups in each SDCDPS molecule, when sulfonated monomer and non-sulfonated monomer mol ratio higher (SDCDPS/DCDPS＞0.6), the PBPSH film is stable existence at room temperature only, in hot water more than 80 ℃, will dissolve.So; The shared mol ratio of sulfonated monomer that can be used for the PBPSH polyether sulfone proton exchange membrane material under the hot conditions should not surpass 0.4, and the membranous sub-conductivity of the PBPSH under this condition and Nafion
film is compared does not have clear superiority.
Summary of the invention
Technical problem
In order to overcome the problem that prior art exists, the purpose of this invention is to provide a kind of PEM and preparation method thereof, said PEM has excellent proton conductivity, high mechanical properties and high stability and with low cost.
Technical scheme
The present invention provides a kind of PEM; It is characterized in that said PEM is to process greater than the blend of the sulfonated polyether sulfone below 0 and 60% more than 60% and less than 100% sulfonated polyether-ether-ketone and sulfonation degree by sulfonation degree; Wherein the ratio of sulfonated polyether-ether-ketone in blend is 30～50 quality %, and the ratio of sulfonated polyether sulfone in blend is 50～70 quality %.
In PEM of the present invention, the sulfonation degree of preferred sulfonated polyether-ether-ketone is 60～90%.
In PEM of the present invention, the sulfonation degree of preferred sulfonated polyether sulfone is 30～60%.
The present invention also provides a kind of method for preparing PEM, said method comprising the steps of:
The preparation sulfonation degree is greater than the sulfonated polyether sulfone below 0 and 60% more than 60% and less than 100% sulfonated polyether-ether-ketone and sulfonation degree;
With the sulfonated polyether sulfone of the sulfonated polyether-ether-ketone of 30～50 quality % and 50～70 quality % in polar solvent blend to form coating solution;
Polar solvent in the coating solution is evaporated to form primary membrane; With
Primary membrane is soaked in acid solution or water or boils to obtain PEM.
In the method for the invention, the sulfonation degree of preferred sulfonated polyether-ether-ketone is 60～90%.
In the method for the invention, the sulfonation degree of preferred sulfonated polyether sulfone is 30～60%.
In PEM of the present invention and preparation method thereof, sulfonated polyether-ether-ketone and sulfonated polyether sulfone blend mass ratio range are 30～50 quality % for the sulfonated polyether-ether-ketone proportion.The sulfonated polyether-ether-ketone mass ratio is lower than at 30% o'clock, and blend film proton conductivity performance reduces; The sulfonated polyether-ether-ketone mass ratio is higher than at 50% o'clock, and blend film high-temperature stability variation possibly be dissolved in more than 60 ℃ in the hot water.
In addition, the sulfonation degree of sulfonated polyether sulfone is below 60%, if sulfonation degree surpasses 60%, blend film will be dissolved in hot water more than 80 ℃, considers the proton conductivity that improves blend film, and the sulfonation degree of sulfonated polyether sulfone is best in 30～60% scopes.The sulfonation degree of sulfonated polyether-ether-ketone is more than 60%; The sulfonated polyether-ether-ketone sulfonation degree is lower than at 60% o'clock; The blend film proton conductivity is lower than business-like Nafion
film; The sulfonation degree of sulfonated polyether-ether-ketone is best in 60～90% scopes; Because when sulfonation degree is 60～90%, the sulfonated polyether-ether-ketone proton conductivity is higher.
Beneficial effect
In blend film of the present invention; Because sulfonated polyether-ether-ketone is similar on chemical constitution with sulfonated polyether sulfone; Be fragrant trunk polymer, and all contain a large amount of sulfonic groups, therefore have good mutual cooperative effect between two kinds of polymer in blend film of the present invention.In blend film of the present invention, two kinds of polymer phase capacitives are fine, show as to form upward transparent blend film of macroscopic view.Because their compatibility is good, can think that two kinds of polymer evenly disperse in the blend film, blend film has the character of stable homogeneous.In addition, because the intermolecular force between the strand sulfonic acid group of two kinds of polymer is stronger, blend film has good mechanical strength.Equally; Because the mutual cooperative effect of two kinds of polymer; Performances such as the stability of blend film of the present invention (high high-temp stability and chemical stability), mechanical strength and proton conductivity not only obviously are superior to independent sulfonated polyether-ether-ketone film and sulfonated polyether sulfone film, and significantly are superior to business-like Nafion
film and prepare simple, with low cost.
Embodiment
The preparation method of SPEEK is shown in scheme 1; According to Mass Calculation; Take by weighing 1 part of PEEK (commercially produced product, model: VICTREX 450P) in 20～100 part of 98% concentrated sulfuric acid, after room temperature to 60 ℃ vigorous stirring is reacted 2～24 hours; Product is poured in the big water gaging precipitates, can obtain sulfonation degree and be 60～100% SPEEK.
Scheme 1PEEK sulfonating reaction prepares SPEEK
Sulfonation degree is that the preparation of 0～60% PBPSH is divided into 3 step schemes and carries out: 1) shown in scheme 2; Calculate according to molal quantity; Take by weighing 1 part of dichloro diphenyl sulfone (DCDPS) monomer and add in 1～5 part of 20～30% oleum, react and be poured in the frozen water after 2～6 hours, add a large amount of sodium chloride salts and separate out sulfonation dichloro diphenyl sulfone (SDCDPS); Before carrying out polycondensation reaction, use NaOH that SDCDPS is converted into sodium-salt type SDCDPS; 2) shown in scheme 3, with sodium-salt type SDCDPS, DCDPS, 4,4 '-'-biphenyl diphenol (BP) according to the certain mol proportion mixed dissolution in polar nonaqueous solvent; Like N, N '-dimethyl formamide (DMF), N, N '-dimethylacetylamide (DMAC) (N; The N-dimethylacetylamide) and in the N-methyl pyrrolidone (NMP), adds 1～2 times to the alkali of monomer molar number, like sodium carbonate, potash, NaOH etc.; 100～230 ℃ of polycondensation reactions 19～72 hours; Obtain PBPSNa sodium-salt type sulfonated polyether sulfone,, can obtain the PBPSNa of a series of different sulfonation degree through changing the mol ratio of SDCDPS and DCDPS; 3) shown in scheme 4, PBPSNa was boiled 0.5～2 hour in a large amount of 0.5～2.0M dilute sulfuric acids, PBPSNa is converted into PBPSH, again with PBPSH in a large amount of pure water, boil 1 hour subsequent use.The weight average molecular weight range of PBPSH is 10,000～200,000.
Scheme 2DCDPS sulfonating reaction prepares SDCDPS
Scheme 3SDCDPS, DCDPS and BP polycondensation reaction prepare sodium-salt type sulfonated polyether sulfone PBPSNa
Scheme 4 sodium-salt type sulfonated polyether sulfone PBPSNa are converted into acid type sulfonated polyether sulfone PBPSH
The preparation of blend film is carried out according to following method: the SPEEK of different sulfonation degree and PBPSH are dissolved in DMF, DMAc, the NMP isopolarity solvent after according to certain mixed, pour into evaporating solvent film forming in the glass mold.Obtained the product film in 1 hour through placing pure water to boil film after the vacuumize.Also can carry out: the SPEEK of different sulfonation degree and PBPSNa are dissolved in DMF, DMAc, the NMP isopolarity solvent after according to certain mixed according to following method; Pour into evaporating solvent film forming in the glass mold; Through placing the film taking-up 0.5～2mol/L dilute sulfuric acid to boil 1～2 hour after the vacuumize, place pure water to boil again and obtained the product film in 1 hour.
Below, specify the present invention through embodiment, but the invention is not restricted to described embodiment.
The method of testing of the performance of the PEM for preparing among the embodiment is at first described.
1. the method for testing of proton conductivity:
Adopt two electrode methods to measure the resistance R of film under the different temperatures saturated humidity.Calculate the proton conductivity of membrane then through formula (1).
σ＝l/RA (1)
L and A are respectively thickness (cm) and the cross-sectional area (cm that is clipped in two interelectrode films in the formula (1)
2).
Be cut into wide 1cm to film, long 2～3cm's is rectangular.During test, be fastened on film between two stainless steel electrodes.Two distance between electrodes are 1cm.One end of stainless steel electrode is connected with electrochemical workstation through lead.Test electrode that assembles and film to be measured are placed in the airtight rustless steel container that certain water gaging is housed.Bottom heating from container.At the upper and lower two parts of container a thermocouple is housed respectively, tests the temperature of bottom water and the saturated gas temperature of film to be measured present position respectively.Relative humidity in the control closed container is 100%.When not heating to closed container, what record with electrochemical workstation is film resistance at room temperature; To the closed container heating, when the thermocouple displays temperature at film place is 80 ℃, measure the resistance of film through electrochemical workstation.Electrochemical workstation is the ZAHNER ZENNIUM that Germany produces, and model is CS350, and scanning frequency is 2 * 10
6～0.05Hz.
2. tensile strength:
According to GB GB1039-79 and GB1040-79 [State Bureau of Technical Supervision of the People's Republic of China (PRC); GB1040-79; State Standard of the People's Republic of China, Beijing: China Standard Press, 1979～05～01)] applying electronic universal testing machine (DNS10) is measured the tensile strength of film.
Embodiment 1
(1) 6 gram PEEK solids is dissolved in the concentrated sulfuric acid of 300 grams 98%; 60 ℃ of following vigorous stirring, react after 7 hours, product is poured in a large amount of pure water obtain fibery precipitate; After being neutrality with pure water cyclic washing to the aqueous solution; 80 ℃ of following forced air dryings 24 hours, obtain the fibrous solid of golden yellow SPEEK, sulfonation degree is about 90%.
(2) 28.7 gram DCDPS white powders are dissolved in 60mL 30% oleum, reacted 6 hours down at 110 ℃, product pours in the 400mL frozen water after being cooled to room temperature.Add 180 gram sodium chloride salts again and separate out the white powder deposition; After the filtration deposition is dissolved in the 400mL pure water; Regulate pH value to 6～7 with the 2M sodium hydrate aqueous solution; Add 180 gram sodium chloride salts again and separate out SDCDPS white powder deposition, will be deposited in 120 ℃ of following vacuumizes 48 hours after the filtration, obtain SDCDPS white powder solid.
(3) take by weighing 5.1732 gram DCDPS, 5.1572 gram SDCDPS, 5.1608 gram BP respectively, be dissolved in the 30mL N-methyl pyrrolidone (NMP), add 4.4050 gram sodium carbonate and 15mL toluene again.Reaction system obtains the dark-brown thick liquid 180 ℃ of following sustained responses 48 hours.Product is poured into and separates out the fibrous deposition of light brown in a large amount of pure water, obtains PBPSNa in 48 hours through fully washing back 120 ℃ of dryings under vacuum.
(4) take by weighing 0.5 gram SPEEK and PBPSNa respectively, be dissolved in 15mL N, process casting solution in the N-dimethylacetylamide (DMAc), be poured in the glass mold, 60 ℃ down dry 24 hours with 120 ℃ of vacuum under drying 24 hours.Mold cools down to room temperature, is soaked demoulding in pure water, film was soaked under the room temperature in the 1M sulfuric acid solution 12～72 hours or in the 1mol/L dilute sulfuric acid, boiled 2 hours.Repeatedly remove sulfuric acid residual in the film with the pure water washing by soaking again, obtain the blend PEM.In order to compare, prepare SPEEK film (sulfonation degree is 90%) and PBPSH film (sulfonation degree is 35%) with the manufacture craft identical with blend film.
It is that 90% SPEEK and sulfonation degree are 35% PBPSH that the blend film of preparation contains sulfonation degree, and blend mass ratio SPEEK accounts for 50%.Prepared PEM mechanical performance of present embodiment and proton conductivity are as shown in table 1:
The SPEEK film of table 1 embodiment 1, PBPSH film, blend film and Nafion
115 film properties relatively
a
Annotate:
aProton conductivity is tested in the pure water environment;
bFilm is dissolved in 80 ℃ of hot water.
Can find out that from table 1 this film has fabulous thermal stability and chemical stability, can keep higher mechanical strength down at 80 ℃.The purer PBPSH film of the conductance of blend film under 80 ℃ has improved 31%, has improved 57% than Nafion
115 films.
Embodiment 2
To prepare SPEEK and PBPSNa with embodiment 1 identical preparation method; And to prepare blend film with embodiment 1 identical method; It is that 90% SPEEK and sulfonation degree are 35% PBPSH that prepared blend film contains sulfonation degree, and difference is that both blend mass ratio SPEEK account for 30%.
Prepared PEM mechanical performance of present embodiment and proton conductivity are as shown in table 2:
The SPEEK film of table 2 embodiment 2, PBPSH film, blend film and Nafion
115 film properties relatively
a
Annotate:
aProton conductivity is tested in the pure water environment;
bFilm is dissolved in 80 ℃ of hot water.
Can find out that from table 2 because SPEEK proportion in blend film is lower, the blend film performance is close with the PBPSH film properties.This film has fabulous thermal stability and chemical stability; 80 ℃ of proton conductivities have improved 10% than PBSH film, have improved 32% than Nafion under the equal conditions
115 films.
Embodiment 3
To prepare SPEEK and PBPSNa with embodiment 1 identical preparation method, the sulfonating reaction time shortened to 4 hours when difference was to prepare SPEEK, obtained the SPEEK sulfonation degree and was about 60%.And preparing blend film with embodiment 1 identical method, it is that 60% SPEEK and sulfonation degree are 35% PBPSH that prepared blend film contains sulfonation degree, and both blend mass ratio SPEEK account for 50%.
Prepared PEM mechanical performance of present embodiment and proton conductivity are as shown in table 3:
The SPEEK film of table 3 embodiment 3, PBPSH film, blend film and Nafion
115 film properties relatively
a
Annotate:
aProton conductivity is tested in the pure water environment.
Can find out that from table 3 proton conductivity of blend film of the present invention is equivalent to the PBPSH film basically, but the mechanical strength of blend film has improved about 24% than pure PBPSH film strength.
Embodiment 4
To prepare SPEEK with embodiment 1 identical preparation method, the sulfonating reaction time shortened to 4 hours when difference was to prepare SPEEK, obtained the SPEEK sulfonation degree and was about 60%.To prepare PBPSNa with embodiment 1 identical preparation method; Difference is to take by weighing respectively 1.5966 gram DCDPS, 4.1130 gram SDCDPS, 2.5804 gram BP; Be dissolved in the 30mL N-methyl pyrrolidone (NMP); Add 4.4050 gram sodium carbonate and 15mL toluene again, 190 ℃ are reacted the PBPSNa that obtained sulfonation degree 60% in 48 hours down.And preparing blend film with embodiment 1 identical method, it is that 60% SPEEK and sulfonation degree are 60% PBPSH that prepared blend film contains sulfonation degree, and both blend mass ratio SPEEK account for 50%.
Prepared PEM mechanical performance of present embodiment and proton conductivity are as shown in table 4:
The SPEEK film of table 4 embodiment 4, PBPSH film, blend film and Nafion
115 film properties relatively
a
Annotate:
aProton conductivity is tested in the pure water environment.
bFilm is dissolved in 80 ℃ of hot water
Blend film of the present invention is because the mutual synergy of SPEEK and two kinds of materials of PBPSH has improved proton conductivity and tensile strength, and these performances all are superior to independent SPEEK and PBPSH film.In addition, blend film of the present invention (80～120 ℃) dimensional stability under hot conditions is also better.
Compare with present business-like Nafion
film, blend PEM of the present invention has following advantage:
(1) SPEEK and PBPSH contain a large amount of sulfonic acid groups; Under uniform temp and damp condition, the blend film proton conductivity is more than or equal to Nafion
film.
(2) because the intermolecular force between SPEEK and the PBPSH strand sulfonic acid group is stronger, blend film has good mechanical strength.
(3) blend film (80～120 ℃) stability under hot conditions is also better.
In addition; The blend film raw material of SPEEK of the present invention and PBPSH is easy to be easy to get, processing technology is simpler than perfluoro sulfonic acid membrane; Therefore the PEM cost of processing is low; Every square metre of cost is no more than 80 dollars, and Nafion
every square metre of price of film is up to 500～800 dollars.
Industrial usability
PEM of the present invention goes for PEM water electrolysis and Proton Exchange Membrane Fuel Cells.
Claims (6)
1. PEM; It is characterized in that: said PEM is to process greater than the blend of the sulfonated polyether sulfone below 0 and 60% more than 60% and less than 100% sulfonated polyether-ether-ketone and sulfonation degree by sulfonation degree; Wherein the ratio of sulfonated polyether-ether-ketone in blend is 30～50 quality %; And the ratio of sulfonated polyether sulfone in blend is 50～70 quality %, and wherein said sulfonated polyether sulfone is expressed from the next:
2. PEM according to claim 1 is characterized in that: the sulfonation degree of sulfonated polyether-ether-ketone is 60～90%.
3. PEM according to claim 1 is characterized in that: the sulfonation degree of sulfonated polyether sulfone is 30～60%.
4. method for preparing the described PEM of claim 1 said method comprising the steps of:
The preparation sulfonation degree is greater than the sulfonated polyether sulfone below 0 and 60% more than 60% and less than 100% sulfonated polyether-ether-ketone and sulfonation degree;
With the sulfonated polyether sulfone of the sulfonated polyether-ether-ketone of 30～50 quality % and 50～70 quality % in polar solvent blend to form coating solution;
Polar solvent in the coating solution is evaporated to form primary membrane; With
Primary membrane is soaked in acid solution or water or boils to obtain PEM.
5. method according to claim 4 is characterized in that: the sulfonation degree of sulfonated polyether-ether-ketone is 60～90%.
6. method according to claim 4 is characterized in that: the sulfonation degree of sulfonated polyether sulfone is 30～60%.
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| WO2022206039A1 (en) | 2021-03-29 | 2022-10-06 | 浙江汉丞新能源有限公司 | Composite membrane of special highly-enhanced fluorine-containing proton or ion exchange membrane, composite membrane electrode, special highly-enhanced fluorine-containing chlor-alkali battery membrane, special release membrane, and preparation method therefor |
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| KR101344686B1 (en) * | 2011-03-18 | 2013-12-26 | 한국과학기술연구원 | Electrolyte membrane for a fuel cell comprising the blend of polymers with different sulfonation degree, membrane-electrode assembly, and a fuel cell comprising the same |
| CN102329432A (en) * | 2011-07-26 | 2012-01-25 | 中国科学院长春应用化学研究所 | Method for preparing sulfonic acid polymer proton exchange membrane |
| CN108123088B (en) * | 2016-11-26 | 2020-03-10 | 中国科学院大连化学物理研究所 | Application of sulfonated polyether ketone ion exchange membrane in zinc-silver battery |
| CN106887628A (en) * | 2017-01-13 | 2017-06-23 | 杭州聚力氢能科技有限公司 | Polyamide/sulfonated polyether-ether-ketone compound proton exchange membrane |
| CN108912361B (en) * | 2018-07-16 | 2020-11-24 | 中国地质大学（武汉） | Method for constructing efficient proton transfer channel in proton exchange membrane |
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| DMFC用PES/SPEEK共混阻醇质子交换膜;黄绵延等;《物理化学学报》;20070131;第23卷(第1期);全文 * |
| SPEEK/PES-C、SPEEK/SPES-C共混质子交换膜研究;高启君等;《高分子学报》;20090131(第1期);全文 * |
| 高启君等.SPEEK/PES-C、SPEEK/SPES-C共混质子交换膜研究.《高分子学报》.2009,(第1期),摘要，第45页第2栏第3段至第46页第1段. |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2022206039A1 (en) | 2021-03-29 | 2022-10-06 | 浙江汉丞新能源有限公司 | Composite membrane of special highly-enhanced fluorine-containing proton or ion exchange membrane, composite membrane electrode, special highly-enhanced fluorine-containing chlor-alkali battery membrane, special release membrane, and preparation method therefor |
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