CN101719553A - Binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) and preparation method thereof - Google Patents

Abstract

The invention relates to a binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) and a preparation method thereof. The PEM comprises the following components in percentage by weight: 80-99% of SPEEK with the vulcanization degree being 40-80%: and 1-20% of binary doped solid:, wherein the binary doped solid comprises cerium oxide or yttrium oxide and phosphotungstic acid in a mol rate of 1:(1-3).

Description

Binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) and preparation method thereof

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:

$V_1=\frac{(1-C)M-{\mathrm{\ρ}}_2{V}_{2}C}{{\mathrm{\ρ}}_{1}C}$

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:

$W=\frac{{\mathrm{mM}}_1\mathrm{KX}}{M_2+M_{1}K}$

$N=\frac{m{M}_{2}X}{M_2+M_{1}K}$

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:

$V_1=\frac{(1-C)M-{\mathrm{\ρ}}_2{V}_{2}C}{{\mathrm{\ρ}}_{1}C}$

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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