CN101719553A - Binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) and preparation method thereof - Google Patents
Binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) and preparation method thereof Download PDFInfo
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- CN101719553A CN101719553A CN200910198236A CN200910198236A CN101719553A CN 101719553 A CN101719553 A CN 101719553A CN 200910198236 A CN200910198236 A CN 200910198236A CN 200910198236 A CN200910198236 A CN 200910198236A CN 101719553 A CN101719553 A CN 101719553A
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- 239000012528 membrane Substances 0.000 title claims abstract description 48
- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 35
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 26
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 19
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 abstract description 5
- 229920002465 poly[5-(4-benzoylphenoxy)-2-hydroxybenzenesulfonic acid] polymer Polymers 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000000463 material Substances 0.000 description 26
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 239000011521 glass Substances 0.000 description 16
- 239000002131 composite material Substances 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 11
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 4
- 244000144730 Amygdalus persica Species 0.000 description 4
- 235000006040 Prunus persica var persica Nutrition 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- 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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Abstract
本发明涉及二元掺杂改性磺化聚醚醚酮SPEEK质子交换膜及其制备方法。该质子交换膜的组成及质量百分比为：磺化度为40％-80％的磺化聚醚醚酮 80％-99％，二元掺杂固体 1％-20％，所述的二元掺杂固体为氧化铈或氧化钇和磷钨酸，其中氧化铈或氧化钇与磷钨酸摩尔比为1∶(1～3)。
The invention relates to a binary doping modified sulfonated polyether ether ketone SPEEK proton exchange membrane and a preparation method thereof. The composition and mass percentage of the proton exchange membrane are: 80%-99% of sulfonated polyether ether ketone with a sulfonation degree of 40%-80%, 1%-20% of binary doped solids, the binary doped The heterosolid is cerium oxide or yttrium oxide and phosphotungstic acid, wherein the molar ratio of cerium oxide or yttrium oxide to phosphotungstic acid is 1: (1-3).
Description
The technology neighborhood
The present invention relates to binary doped modified sulfonated polyether-ether-ketone SPEEK proton exchange membrane and preparation method thereof, particularly a kind of cerium oxide or yittrium oxide and the binary doped modified sulfonated polyether-ether-ketone SPEEK of phosphotungstic acid proton exchange membrane and preparation method thereof.
Background technology
Polyether-ether-ketone (SPEEK) material owing to have high mechanical properties, thermal stability and chemical stability become the primary study material of direct methanol fuel cell proton exchange membrane preferably.With the sulfonated reagent such as the concentrated sulfuric acid PEEK is carried out sulfonation, sulfonic acid group is incorporated on the PEEK main chain, because hydrophobic existence mutually such as phenyl ring, ehter bond on sulfonic group aqueous favoring and the polymer backbone, can make the SPEEK material have certain proton conductivity, and the relatively low cost of SPEEK material, higher mechanical strength, heat-resistant stability and excellent alcohol-rejecting ability can satisfy the requirement of fuel cell to proton exchange membrane material.But the sulfonation degree of this kind material (DS) can directly influence the performance of proton exchange membrane each side, the SPEEK proton exchange membrane of low DS has mechanical strength preferably, alcohol-rejecting ability, thermo-chemical stability, but because sulfonic negligible amounts, two be separated not obvious, its proton conductivity is not high, the realization of fuel cell chemical cycle reaction and the efficient of fuel cell have been hindered, though and the SPEEK proton exchange membrane of high DS has higher proton conductivity, but its mechanical strength reduces, water absorption rate and swellbility are too high, at high temperature SPEEK can degrade in methyl alcohol, has a strong impact on the stability of film and the life-span of fuel cell.Because there is conflicting effect in sulfonation degree to the proton exchange membrane material performance, on the conceptual design of SPEEK proton exchange membrane, need take all factors into consideration the mode of SPEEK sulfonation degree and modification usually, can not attend to one thing and lose sight of another.
Summary of the invention
One of purpose of the present invention is to provide the binary doped modified sulfonated polyether-ether-ketone SPEEK of a kind of cerium oxide or yittrium oxide and phosphotungstic acid proton exchange membrane.
Two of purpose of the present invention is to provide the preparation method of this proton exchange membrane.
According to pertinent literature, phosphotungstic acid (TPA) is as a kind of heteropoly acid, a large amount of adsorbed water, the crystallization water and constitution water are contained in inside, and the existence meeting of a large amount of hydrones is played facilitation to the proton conduction of proton exchange membrane, so phosphotungstic acid can significantly improve the proton conductivity of proton exchange membrane.And thereby cerium oxide or yittrium oxide can make more fine and close its alcohol-rejecting ability that improves of SPEEK proton exchange membrane structure, and better dispersed in the SPEEK film of nano level cerium oxide or yittrium oxide, are difficult for taking place heavy phenomenon such as poly-.
According to above-mentioned theory, the present invention adopts following technical scheme:
A kind of binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) is characterized in that the composition of this proton exchange membrane and mass percent are:
Sulfonation degree is the sulfonated polyether-ether-ketone 80%-99% of 40%-80%,
Binary doped solid 1%-20%,
Described binary doped solid is cerium oxide or yittrium oxide and phosphotungstic acid, and wherein cerium oxide or yittrium oxide and phosphotungstic acid mol ratio are 1: (1～3).
The above-mentioned cerium oxide or the grain diameter of yttria particles are at 10-200nm.
A kind of method for preparing above-mentioned binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM), the concrete steps that it is characterized in that this method are: composition according to claim 1 and quality per distribution ratio, with sulfonation degree is that the sulfonated polyether-ether-ketone of 40%-80%, binary doped solid dispersed are in the system membrane solvent, be mixed with the preparation liquid that solid content is 5%-40%, sonicated can be dispersed in the system membrane solvent sulfonated polyether-ether-ketone and binary doped solid; With this preparation liquid casting film-forming, after drying, the cooling, take off film then, promptly obtain binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM).
Above-mentioned system membrane solvent is acetone and N, N-dimethylacetylamide, N, and the mixed solution that dinethylformamide, dimethyl sulfoxide (DMSO) or oxolane are formed, wherein the computing formula of the volume of the acetone and the second component solvent is as follows:
Wherein, ρ
1Be the density of the second component solvent; C is the solid content of this preparation liquid; M is the gross mass of sulfonated polyether-ether-ketone, binary doped solid; ρ
2, V
2Be respectively the density and the volume of acetone.
Illustrate:
1. sulfonated polyether-ether-ketone SPEEK sulfonation degree (DS): the sulfonic acid group number that the every repetitive of SPEEK is contained.According to the reaction time difference, can prepare the sulfonated polyether-ether-ketone of different DS.In this experiment, the sulfonation degree of SPEEK records by nulcear magnetic resonance (NMR).
2. solid content: sulfonated polyether-ether-ketone SPEEK, cerium oxide or yittrium oxide and phosphotungstic acid H
3PW
12O
40The percentage composition of the gross mass of three components in film making solution.
1. phosphotungstic acid H
3PW
12O
40The quality of quality and rare-earth oxide cerium oxide or yittrium oxide, the mole proportioning of root a tree name cerium oxide or yittrium oxide and phosphotungstic acid, the total doping of the gross mass of three components and solids is calculated.Phosphotungstic acid H
3PW
12O
40Quality N (g) computing formula of quality W (g) and rare-earth oxide cerium oxide or yittrium oxide is as follows:
Wherein, m (g) is sulfonated polyether-ether-ketone SPEEK, cerium oxide CeO
2Or yittrium oxide Y
2O
3With phosphotungstic acid H
3PW
12O
40The gross mass of three components, X is cerium oxide CeO
2Or yittrium oxide Y
2O
3With H
3PW
12O
40The total doping of solid, K is H
3PW
12O
40With Y
2O
3Or CeO
2Mol ratio, M
1(g/mol), M
2(g/mol) be H respectively
3PW
12O
40And rare-earth oxide Y
2O
3Or CeO
2Molal weight.
The advantage of modification sulphonation polyetheretherketoneproton proton exchange film of the present invention and preparation method thereof is: 1, adopt the SPEEK of medium sulfonation degree as basis material, too high to overcome the water absorption rate that highly sulfonated SPEEK exists, the shortcoming of composite membrane less stable, and guarantee that composite membrane has certain water absorption rate; 2, by rare-earth oxide yittrium oxide and the binary doped mode of phosphotungstic acid, make between SPEEK matrix and this dopant material acid-base function takes place, to improve the combination property of composite membrane.
Description of drawings
Fig. 1 is the 61.79%SPEEK nmr spectrum for DS;
Fig. 2 is the 68.02%SPEEK nmr spectrum for DS;
Embodiment
Embodiment one: the compositing formula and the preparation technology of present embodiment are as follows:
1. compositing formula
A. composite membrane basis material: DS is 68.02% SPEEK material, and mass percent is 90%.
B. binary doped solid: nano Ce O
2, H
3PW
12O
40, mass percent is 10%, wherein CeO
2And H
3PW
12O
40Mol ratio is 1: 1.
2.DS be the synthetic of 68.02% SPEEK material: 20g PEEK powder, the 800ml concentrated sulfuric acid are joined in the there-necked flask of 1L, at 60 ℃ of following mechanical agitation reaction 9h, behind the question response liquid cool to room temperature, reactant liquor by glass funnel, is poured in the mixture of ice and water of 4.5L, after the cooling, with a large amount of deionized water rinsing 6 times, use the deionized water standing over night of 4.5L then, use the deionized water rinse again 3 times, filter out peach SPEEK solid, with product at 100 ℃ of following vacuumize 24h.
3. the preliminary treatment of material: the SPEEK material after will shredding descends dry 24h at 100 ℃, and phosphotungstic acid behind the porphyrize and nano-cerium oxide are descended dry 48h at 80 ℃.
4. the preparation of composite membrane: take by weighing 1.3502g SPEEK, 0.0085g CeO
2Place the ground beaker, pipette 10mlDMF with pipette again and add in the above-mentioned port grinding bottle, 24h is stirred in the sealing back, adds 5ml acetone again, 0.1415g H
3PW
12O
40, continue stirring 2h, ultrasonic again 1h gets the 6.6ml preparation liquid and waters and cast from 10cm * 6cm glass plate, glass plate is dry 20h under 50 ℃ earlier, behind 120 ℃ of dry 4h, takes out from baking oven then, after treating that it naturally cools to room temperature, on glass plate, pour small amount of deionized water into and take off film, obtain.
The water absorption rate of pure SPEEK film under 30 ℃ is 20.41%, and the methanol crossover coefficient is 9.20 * 10
-7Cm
2/ s, proton conductivity are 3.20 * 10
-3S/cm; This composite membrane water absorption rate is 17.92%, and the methanol crossover coefficient is 8.35 * 10
-7Cm
2/ s, proton conductivity are 3.01 * 10
-3S/cm.
Embodiment two: the compositing formula and the preparation technology of present embodiment are as follows:
1. compositing formula
A. composite membrane basis material: DS is 61.79% SPEEK material, and mass percent is 85%.
B. binary doped solid: nanometer Y
2O
3, H
3PW
12O
40, mass percent is 15%, wherein Y
2O
3And H
3PW
12O
40Mol ratio is 1: 1.
2.SPEEK synthetic: 25g PEEK powder, the 500ml concentrated sulfuric acid are joined in the there-necked flask of 1L, at 60 ℃ of following mechanical agitation reaction 6h, behind the question response liquid cool to room temperature, reactant liquor by glass funnel, is poured in the mixture of ice and water of 4.5L, after the cooling, with a large amount of deionized water rinsing 6 times, use the deionized water standing over night of 4.5L then, use the deionized water rinse again 3 times, filter out peach SPEEK solid, with product at 100 ℃ of following vacuumize 24h.
3. the preliminary treatment of material: the SPEEK material after will shredding descends dry 24h at 120 ℃, and phosphotungstic acid behind the porphyrize and nano yttrium oxide are descended dry 36h at 80 ℃.
4. the preparation of composite membrane: take by weighing 1.2748g SPEEK, 0.0163g Y
2O
3Place the ground beaker, pipette 10mlDMF with pipette again and add in the above-mentioned port grinding bottle, 8h is stirred in the sealing back, adds 5ml acetone again, 0.2085g H
3PW
12O
40, continue to stir 4h, ultrasonic again 2h, get the 6.6ml preparation liquid and water and cast from 10cm * 6cm glass plate, glass plate is earlier at 50 ℃ of dry 20h down, then behind 120 ℃ of dry 4h, from baking oven, take out, treat that it naturally cools to room temperature after, on glass plate, pour small amount of deionized water into and take off film.
The water absorption rate of pure SPEEK film under 30 ℃ is 18.41%, and the methanol crossover coefficient is 8.85 * 10
-7Cm
2/ s, proton conductivity are 1.84 * 10
-3S/cm; The water absorption rate of this composite membrane is 12.92%, and the methanol crossover coefficient is 6.89 * 10
-7Cm
2/ s, proton conductivity are 1.09 * 10
-3S/cm.
Embodiment three: the compositing formula and the preparation technology of present embodiment are as follows:
1. compositing formula
A. composite membrane basis material: DS is 61.79% SPEEK material, and mass percent is 90%.
B. binary doped solid: nanometer Y
2O
3, H
3PW
12O
40, mass percent is 10%, wherein Y
2O
3And H
3PW
12O
40Mol ratio is 1: 2.
2.SPEEK synthetic: 25g polyether-ether-ketone PEEK powder, the 500ml concentrated sulfuric acid are joined in the there-necked flask of 1L, at 60 ℃ of following mechanical agitation reaction 6h, behind the question response liquid cool to room temperature, reactant liquor by glass funnel, is poured in the mixture of ice and water of 4.5L, after the cooling, with a large amount of deionized water rinsing 6 times, use the deionized water standing over night of 4.5L then, use the deionized water rinse again 3 times, filter out peach SPEEK solid, with product at 100 ℃ of following vacuumize 24h.
3. the preliminary treatment of material: the SPEEK material after will shredding descends dry 24h at 120 ℃, and phosphotungstic acid behind the porphyrize and nano yttrium oxide are descended dry 48h at 80 ℃.
4. the preparation of composite membrane: take by weighing 1.3502g SPEEK, 0.0057g Y
2O
3Place the ground beaker, pipette 10mlDMA with pipette again
CAdd in the above-mentioned port grinding bottle, 10h is stirred in the sealing back, adds 5ml acetone again, 0.1441g H3PW12O40, continue to stir 2h, ultrasonic again 1h gets the 6.6ml preparation liquid and waters and cast from 10cm * 6cm glass plate, and glass plate is earlier at 50 ℃ of dry 20h down, then behind 120 ℃ of dry 4h, from baking oven, take out, treat that it naturally cools to room temperature after, on glass plate, pour small amount of deionized water into and take off film.
The water absorption rate of pure SPEEK film under 30 ℃ is 18.41%, and the methanol crossover coefficient is 8.85 * 10
-7Cm
2/ s, proton conductivity are 1.84 * 10
-3S/cm; The water absorption rate of this composite membrane is 16.77%, and the methanol crossover coefficient is 5.10 * 10
-7Cm
2/ s, proton conductivity are 2.74 * 10
-3S/cm.
Embodiment four: the compositing formula and the preparation technology of present embodiment are as follows:
1. compositing formula
A. composite membrane basis material: DS is 61.79% SPEEK material, and mass percent is 85%.
B. binary doped solid: nanometer Y
2O
3, H
3PW
12O
40, mass percent is 15%, wherein Y
2O
3And H
3PW
12O
40Mol ratio is 1: 2.
2.SPEEK synthetic: 25g polyether-ether-ketone PEEK powder, the 500ml concentrated sulfuric acid are joined in the there-necked flask of 1L, at 60 ℃ of following mechanical agitation reaction 6h, behind the question response liquid cool to room temperature, reactant liquor by glass funnel, is poured in the mixture of ice and water of 4.5L, after the cooling, with a large amount of deionized water rinsing 6 times, use the deionized water standing over night of 4.5L then, use the deionized water rinse again 3 times, filter out peach SPEEK solid, with product at 100 ℃ of following vacuumize 24h.
3. the preliminary treatment of material: the SPEEK material after will shredding descends dry 24h at 100 ℃, and phosphotungstic acid behind the porphyrize and nano yttrium oxide are descended dry 48h at 80 ℃.
4. the preparation of composite membrane: take by weighing 1.2750g SPEEK, 0.0083g Y
2O
3Place the ground beaker, pipette 10mlTHF with pipette again and add in the above-mentioned port grinding bottle, 6h is stirred in the sealing back, adds 5ml acetone again, 0.2166g H
3PW
12O
40, continue to stir 2h, ultrasonic again 2h, get the 6.6ml preparation liquid and water and cast from 10cm * 6cm glass plate, glass plate is earlier at 50 ℃ of dry 20h down, then behind 120 ℃ of dry 4h, from baking oven, take out, treat that it naturally cools to room temperature after, on glass plate, pour small amount of deionized water into and take off film.
The water absorption rate of pure SPEEK film under 30 ℃ is 18.41%, and the methanol crossover coefficient is 8.85 * 10
-7Cm
2/ s, proton conductivity are 1.84 * 10
-3S/cm; The water absorption rate of this composite membrane is 16.73%, and the methanol crossover coefficient is 3.79 * 10
-7Cm
2/ s, proton conductivity are 2.33 * 10
-3S/cm.
Claims (4)
1. binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) is characterized in that the composition of this proton exchange membrane and mass percent are:
Sulfonation degree is the sulfonated polyether-ether-ketone 80%-99% of 40%-80%,
Binary doped solid 1%-20%,
Described binary doped solid is cerium oxide or yittrium oxide and phosphotungstic acid, and wherein cerium oxide or yittrium oxide and phosphotungstic acid mol ratio are 1: (1～3).
2. binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) according to claim 1, the grain diameter that it is characterized in that described cerium oxide or yttria particles is at 10-200nm.
3. method for preparing binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) according to claim 1 and 2, the concrete steps that it is characterized in that this method are: composition according to claim 1 and mass percent, with sulfonation degree is that the sulfonated polyether-ether-ketone of 40%-80%, binary doped solid dispersed are in the system membrane solvent, be mixed with the preparation liquid that solid content is 5%-40%, sonicated can be dispersed in the system membrane solvent sulfonated polyether-ether-ketone and binary doped solid; With this preparation liquid casting film-forming, after drying, the cooling, take off film then, promptly obtain binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM).
4. preparation method according to claim 3, it is characterized in that described system membrane solvent is acetone and N, N-dimethylacetylamide, N, the mixed solution that dinethylformamide, dimethyl sulfoxide (DMSO) or oxolane are formed, wherein the volume of the acetone and the second component solvent calculates by following formula:
Wherein, ρ
1Be the density of the second component solvent; C is the gross mass of sulfonated polyether-ether-ketone, binary doped solid for the solid content M of this preparation liquid; ρ
2, V
2Be respectively the density and the volume of acetone.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101908632A (en) * | 2010-07-15 | 2010-12-08 | 上海大学 | Preparation method of ternary doping modified SPEEK proton exchange membrane |
| CN102020781A (en) * | 2010-10-30 | 2011-04-20 | 华南理工大学 | Modified sulfonated poly ether ether ketone (SPEEK) membrane applied to direct methanol fuel cell (DMFC) and preparation method of SPEEK membrane |
| CN103474688A (en) * | 2013-09-22 | 2013-12-25 | 上海大学 | Nano cerium oxide-modified sulfonated polyphenylene sulfide proton exchange membrane and preparation method thereof |
| CN103490084A (en) * | 2013-09-18 | 2014-01-01 | 上海大学 | Ternary doped and modified sulfonate polyphenylene sulfide proton exchange membrane and method for preparing same |
| CN107845760A (en) * | 2017-11-10 | 2018-03-27 | 苏州格瑞动力电源科技有限公司 | Lithium ion battery with barrier film |
| CN111063924A (en) * | 2019-12-27 | 2020-04-24 | 先进储能材料国家工程研究中心有限责任公司 | Transition layer slurry for membrane electrode, preparation method of transition layer slurry, membrane electrode and preparation method of membrane electrode |
| CN118173809A (en) * | 2024-04-28 | 2024-06-11 | 深圳市氢瑞燃料电池科技有限公司 | Enhanced non-fluorine proton exchange membrane and preparation method and application thereof |
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2009
- 2009-11-03 CN CN200910198236XA patent/CN101719553B/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101908632A (en) * | 2010-07-15 | 2010-12-08 | 上海大学 | Preparation method of ternary doping modified SPEEK proton exchange membrane |
| CN102020781A (en) * | 2010-10-30 | 2011-04-20 | 华南理工大学 | Modified sulfonated poly ether ether ketone (SPEEK) membrane applied to direct methanol fuel cell (DMFC) and preparation method of SPEEK membrane |
| CN102020781B (en) * | 2010-10-30 | 2012-05-09 | 华南理工大学 | Modified sulfonated polyether-ether-ketone membrane applied to direct alcohol fuel cell and preparation method thereof |
| CN103490084A (en) * | 2013-09-18 | 2014-01-01 | 上海大学 | Ternary doped and modified sulfonate polyphenylene sulfide proton exchange membrane and method for preparing same |
| CN103490084B (en) * | 2013-09-18 | 2015-10-07 | 上海大学 | Ternary doping modified Sulfonated Polyphenylene Sulfide proton exchange membrane and preparation method thereof |
| CN103474688A (en) * | 2013-09-22 | 2013-12-25 | 上海大学 | Nano cerium oxide-modified sulfonated polyphenylene sulfide proton exchange membrane and preparation method thereof |
| CN107845760A (en) * | 2017-11-10 | 2018-03-27 | 苏州格瑞动力电源科技有限公司 | Lithium ion battery with barrier film |
| CN111063924A (en) * | 2019-12-27 | 2020-04-24 | 先进储能材料国家工程研究中心有限责任公司 | Transition layer slurry for membrane electrode, preparation method of transition layer slurry, membrane electrode and preparation method of membrane electrode |
| CN111063924B (en) * | 2019-12-27 | 2022-10-14 | 先进储能材料国家工程研究中心有限责任公司 | Transition layer slurry for membrane electrode, preparation method of transition layer slurry, membrane electrode and preparation method of membrane electrode |
| CN118173809A (en) * | 2024-04-28 | 2024-06-11 | 深圳市氢瑞燃料电池科技有限公司 | Enhanced non-fluorine proton exchange membrane and preparation method and application thereof |
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