CN101188301A - A proton exchange film for direct carbinol fuel battery and its making method - Google Patents
A proton exchange film for direct carbinol fuel battery and its making method Download PDFInfo
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- CN101188301A CN101188301A CNA2007100323116A CN200710032311A CN101188301A CN 101188301 A CN101188301 A CN 101188301A CN A2007100323116 A CNA2007100323116 A CN A2007100323116A CN 200710032311 A CN200710032311 A CN 200710032311A CN 101188301 A CN101188301 A CN 101188301A
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Abstract
The invention discloses a preparation method of a proton exchange membrane used for a direct methanol fuel cell. The method is realized by that polyether ether ketone is added into concentrated sulfuric acid to carry out sulfonation reaction, thereby obtaining sulfonated polyether ether ketone, then the sulfonated polyether ether ketone is dissolved in organic solvent, N, N (1)-Carbonyldiimidazole is added to stir for one to three hours, coupling agent is mixed for stirring the reaction for 1.5 to 4 hours, then inorganic crosslinking agent is mixed to react under the temperature of 50 to 80 DEG C. Proton conductors are mixed to continue getting the mixed solution of the sulfonated polyether ether ketone or the inorganic crosslinking agent or proton conductors under the temperature. Finally the proton exchange membrane for a direct methanol fuel cell is obtained by that the mixed solution of the sulfonated polyether ether ketone or the inorganic crosslinking agent or proton conductors is/are processed through membrane forming, drying and exuviation. The membrane has the advantages of good methanol diffusion resistance, low cost, high proton conductivity and good water-resistant swelling performance under high temperature. The preparation method is simple, the raw materials have low price, and the production cost is low.
Description
Technical field
The invention belongs to the fuel cell technology field, particularly a kind of direct methanol fuel cell proton exchange membrane and preparation method thereof.
Background technology
Direct methanol fuel cell (DMFC) be with methyl alcohol make fuel, with a kind of fuel cell of oxygen or air oxidant.DMFC not only has the advantage that fuel source is abundant, with low cost, energy density is high, and the used fuel methanol of DMFC do not exist hydrogen/oxygen or air fuel with fuel hydrogen such be difficult to preparation, storage, transportation and uneasy congruent problem; Take the direct feeding manner of fuel during work, need not to add and reform and the humidification processing; Battery pile system simple in structure, the response time is short, and is easy to operate.Therefore, DMFC is considered to the fuel cell that a class has development potentiality and using value in the small-power power application facet.At present, DMFC still adopts the serial perfluoro sulfonic acid membrane of naphthalene fluorine (Nafion) of du pont company production as proton exchange membrane (PEM).Though this class perfluoro sulfonic acid membrane has higher proton conductivity, chemical stability, thermal stability and mechanical strength, when being applied to DMFC, it then has obvious defects.Mainly be costing an arm and a leg of this film, dehydration easily under higher temperature, lower to the concentration difference diffusion and the electromigration diffusion selectivity of first alcohol and water, methyl alcohol is bigger from the permeability that anode is penetrated into negative electrode, thereby make the performance degradation of battery, limited the development and application of DMFC widely.
Therefore, adopt non-fluorine aromatic ring trunk polymer to prepare the focus that novel proton exchange membranes (PEM) is just becoming people's research with good heat resistance.The aromatic ring trunk polymer generally has excellent thermal stability, mechanical stability and chemical stability.After introducing sulfonic group on the aromatic ring, sulfonated polymer has just had higher water stream channel and differential permeability, particularly because the raising of membrane material solubility property has brought the film build method more convenient, that cost is more cheap.At present, being studied more non-fluorine sulfonated polymer is sulfonated polyphenyl imidazoles, SPSF, sulfonated polyimide, sulfonated polyether-ether-ketone (SPEEK) etc.Wherein, sulfonated polyether-ether-ketone (SPEEK) is especially noticeable.Compare with the Nafion film, the sulfonated polyether-ether-ketone film has the proton conductivity suitable with it, higher thermal stability and mechanical performance, and the cost of SPEEK film is much lower, have narrower proton channel, more branched structure and less methanol crossover coefficient, thereby the SPEEK film has been subjected to people's extensive concern in the research of DMFC application facet.Zaidi etc. discover that sulfonation degree at room temperature is that the water absorption rate of the SPEEK film of 60mol.% is 26%, and after sulfonation degree was greater than 70mol.%, the water absorption rate of film sharply increased, and when sulfonation degree reached 80mol.%, the water absorption rate of film reached 120%.And Chang etc. discover that the variation of SPEEK film water absorption rate in 20～60 ℃ temperature range still is smaller, are elevated to after 70 ℃ but work as temperature, and the water absorption rate of film also is rapid increase.Zhang Gaowen etc. introduce inorganic imvite in the SPEEK matrix, find that the water absorbing properties of film reduces, and methanol permeability reaches 10 at normal temperatures
-8Cm
2The order of magnitude of/s, but find also that simultaneously the imvite of mixing significantly decreases the proton conductivity of composite membrane; Nunes adopts sol-gel process to prepare SPEEK/SiO
2, SPEEK/TiO
2And SPEEK/ZrO
2Composite membrane.SiO
2Also the swelling that suppresses polymer molecule is played a role Deng the introducing of inorganic network structure, and inorganic particulate also reduced methanol permeation, but the proton conductivity of composite membrane descends to some extent.Zaidi etc. are incorporated into heteropoly acid PWA in the SPEEK film, find the high-temperature stability of also having improved the proton conduction of film simultaneously of mixing of heteropoly acid, and the proton conductivity of SPEEK/PWA film reaches 0.095S/cm in the time of 100 ℃.But find also that simultaneously the alcohol-rejecting ability that mixes the heteropoly acid composite membrane significantly decreases.
At present, the SPEEK film is used in the industrialization development in DMFC field and is still had following problem:
L, than highly sulfonated SPEEK film not only under higher temperature to the easy swelling of the water capacity, the poor dimensional stability of film, and film also can become fragile, and the mechanical strength of film is reduced; Be not difficult to process film forming and be not soluble in organic solvent, and the proton conductivity of made film is lower, does not satisfy the requirement of DMFC to electrical property than the SPEEK of low sulfonation degree;
2, people are carrying out the SPEEK film in the process of study on the modification, the means of being taked are also comparatively single so far: though only introduce the swelling problem that the inorganic crosslinking structure can solve film in SPEEK, reduce the methanol permeability of film, but also caused the decline of membranous sub-conductive performance; Though can improve membranous sub-conductive performance and only introduce heteropoly acid, can cause the alcohol-rejecting ability of film to descend, and heteropoly acid also face the problem of oozing out;
3, perfect not enough to the research of the preparation technology of compound SPEEK proton exchange membrane and combination property, how improve additive particles in the SPEEK matrix degree of scatter and the composition proportioning of how the to regulate the controlling diaphragm material effectively proton conduction performance that makes film and alcohol-rejecting ability between reach aspects such as optimum balance simultaneously and also have deficiency.
4, the DMFC that people developed so far is still lower with the proton conductivity of proton exchange membrane, and methanol permeability is still higher, and perhaps cost is also expensive, thus the instructions for use that does not also reach DMFC.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of direct methanol fuel cell proton exchange membrane is provided.The features good methanol diffusion resistance of this film, the cost cost is low, proton conductivity is high, the anti-swelling to water under the higher temperature can be good.
Another object of the present invention is to provide the preparation method of described direct methanol fuel cell with proton exchange membrane.
Purpose of the present invention is achieved through the following technical solutions: a kind of direct methanol fuel cell is characterized in that comprising the steps: with the preparation method of proton exchange membrane
(1) calculates by weight, it is to carry out sulfonating reaction in 95～98% the concentrated sulfuric acid that 1 part of polyether-ether-ketone is added to 35～75 parts of weight percent concentration, then taking precipitate is filtered in reactant liquor dilution back, water is washed till the aqueous solution with sediment and is neutral back drying and obtains sulfonated polyether-ether-ketone;
(2) sulfonated polyether-ether-ketone is dissolved in the organic solvent, be made into weight percent concentration and be 10～15% sulfonated polyether-ether-ketone solution, add N, N '-carbonyl dimidazoles (CDI), the N that is added, the mol ratio of sulfonate radical is 1: 2～4 in N '-carbonyl dimidazoles and the sulfonated polyether-ether-ketone; Stir and add the coupling agent stirring reaction after 1～3 hour again and obtained the sulfonated polyether-ether-ketone reactant liquor in 1.5～4 hours, coupling agent that is added and N, the mol ratio of N '-carbonyl dimidazoles is 1: 1;
(3) will be that 1: 5～17 inorganic crosslinking agent joins in the above-mentioned sulfonated polyether-ether-ketone reactant liquor with the sulfonated polyether-ether-ketone weight ratio, reacted 6～12 hours down at 50～80 ℃, adding and sulfonated polyether-ether-ketone weight ratio are 1: 3.5～17 proton conductor then, continue to obtain after reacting 8～14 hours under this temperature the mixed solution of sulfonated polyether-ether-ketone/inorganic crosslinking agent/proton conductor;
(4) with the mixture solution film forming of sulfonated polyether-ether-ketone/inorganic crosslinking agent/proton conductor, drying, demoulding promptly obtains described direct methanol fuel cell proton exchange membrane.
In order to realize the present invention better, the sulfonating reaction condition is 25～60 ℃ of following sulfonating reactions 8～50 hours in the described step (1).
Organic solvent comprises N, N-dimethylacetylamide (DMAc), N, dinethylformamide (DMF) or N-crassitude (NMP) in the described step (2).
Coupling agent is aminopropyltriethoxywerene werene (AS), γ-(2,3-encircles third oxygen) propyl trimethoxy silicane (GPTS), gamma-aminopropyl-triethoxy-silane or N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane in the described step (2).
Inorganic crosslinking agent comprises silicon dioxide (SiO in the described step (3)
2), titanium dioxide (TiO
2), alundum (Al (Al
2O
3), zirconium dioxide (ZrO
2) or silica-based esterification products; Described proton conductor comprises phosphotungstic acid (PWA), silico-tungstic acid (SWA), basic zirconium phosphate (Zr (HPO
4)
2), alpha zirconium phosphate (α-ZrP) or orthophosphoric acid boron (BPO
4) etc.Preferred inorganic crosslinking agent and proton conductor carried out the ultrasonic wave dispersion treatment earlier before adding.
Drying is preferably following dry 24～32 hours at 55～65 ℃ in the described step (4).
Is 1.202 * 10 with proton exchange membrane at 20～80 ℃ proton conductivity by the prepared direct methanol fuel cell of said method
-2～4.238 * 10
-2S/cm, methanol crossover coefficient are 3.14 * 10
-8～9.56 * 10
-7Cm
2/ s.
Direct methanol fuel cell of the present invention can be passed through following processing before use with proton exchange membrane: at rare H
2SO
4Soaked 24 hours in the aqueous solution, remove H residual in the film with deionized water wash again
2SO
4
The present invention is to be matrix with the sulfonated polyether-ether-ketone, introduce inorganic crosslinking agent, proton conductor and coupling agent therein, in the proton conductivity that improves film, reduce the swellbility of film effectively, thereby further reduce the methanol permeability of film, improve power density and the useful life of DMFC.
The present invention compared with prior art has following advantage and beneficial effect:
1, direct methanol fuel cell of the present invention not only has narrower proton channel, more branched structure and less methanol crossover coefficient with proton exchange membrane, and in the sulfonated polyether-ether-ketone base-material, introduce coupling agent, inorganic crosslinking agent and proton conductor simultaneously it is carried out modification, when improving the proton conductivity of film, reduce effectively film in water swellbility and to the methanol permeation performance, also effectively prevented oozing out of proton conductor by the inorganic crosslinking network configuration, in the alcohol-rejecting ability that improves film, also improved the proton conduction performance of film;
2, the present invention adds coupling agent in membrane material, make that the form with covalent bond combines between sulfonated polyether-ether-ketone matrix and the inorganic crosslinking structure, thereby improved the compatibility of two-phase interface well, it is more even to make that also the inorganic crosslinking structure distributes in the sulfonated polyether-ether-ketone matrix, thereby has improved the alcohol-rejecting ability of composite membrane effectively;
3, among the preparation method of the present invention, before adding inorganic crosslinking agent and proton conductor, earlier it is carried out the ultrasonic wave dispersion treatment, thereby avoided the reunion of inorganic crosslinking agent and proton conductor, improved the even degree of scatter of these particles in the sulfonated polyether-ether-ketone matrix well;
4, the present invention is by changing the composition proportioning between inorganic crosslinking agent and the proton conductor, makes novel proton exchange membranes reach the balance of the best between high proton conductivity and low methanol permeability;
5, direct methanol fuel cell of the present invention reaches 10 with proton exchange membrane at 20～80 ℃ proton conductivity
-2The order of magnitude level of S/cm, the methanol crossover coefficient reaches 10
-8～10
-7Cm
2The order of magnitude of/s can satisfy the instructions for use of DMFC;
6, preparation method of the present invention is more simple relatively, and the prices of raw and semifnished materials are cheap, and production cost is relatively low, and its application will be expected effectively to promote the practicability and the development of direct methanol fuel cell.
Description of drawings
Fig. 1 is the temperature variant graph of a relation of the swellbility of different proton exchange membrane.
Fig. 2 is ESEM (SEM) figure of proton exchange membrane section of the present invention.
Fig. 3 is the temperature variant graph of a relation of the proton conductivity of different proton exchange membrane.
Fig. 4 is the temperature variant graph of a relation of the methanol permeability of different proton exchange membrane.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but the working of an invention mode is not limited thereto.
(1) 3 gram polyether-ether-ketone (PEEK) pellets being dissolved in 180 gram weight percent concentrations is in 98% the concentrated sulfuric acid, 30 ℃ of following vigorous stirring, continue sulfonation after 48 hours, reaction solution poured in the frozen water dilute, making the frozen water volume is 5 times of reaction solution, with the reacting liquid filtering taking precipitate of dilution, with distilled water the sediment cyclic washing is neutral back 60 ℃ of following vacuumizes 24 hours until the aqueous solution, obtain sulfonated polyether-ether-ketone (SPEEK);
(2) 3 gram SPEEK are dissolved in the anhydrous N of 27 grams, in the N-dimethylacetylamide (DMAc), are made into 10wt.% solution.Add 0.26 gram N again, N '-carbonyl dimidazoles (CDI), on the CDI and SPEEK that is added-SO
3The mol ratio of H was 1: 4,60 ℃ of stirring reactions 2 hours.Add 0.35 gram aminopropyltriethoxywerene werene (AS) again, AS that is added and the mol ratio of CDI are 1: 1, and obtain the sulfonated polyether-ether-ketone reactant liquor in 2 hours at 60 ℃ of following stirring reactions;
(3) be 5 hydrochloric acid of adding in 1: 17 0.176 gram tetraethyl orthosilicate (TEOS) at mass ratio with sulfonated polyether-ether-ketone, and it is carried out the ultrasonic wave dispersion treatment, join then in the above-mentioned sulfonated polyether-ether-ketone reactant liquor, stirred 8 hours down at 60 ℃, the 0.353 gram phosphotungstic acid (PWA) that will be 1: 8.5 again with the mass ratio of sulfonated polyether-ether-ketone joins in the above-mentioned solution after with the ultrasonic wave dispersion treatment, stirred 12 hours down at 60 ℃, the proportioning that has obtained sulfonated polyether-ether-ketone/silicon dioxide/phosphotungstic acid like this is 85: 5: 10 a mixed solution;
(4) with mixture solution film forming on the mould that glass plate and polyester film surrounded of sulfonated polyether-ether-ketone/silicon dioxide/phosphotungstic acid, drying is 24 hours under 60 ℃, after being cooled to room temperature, demoulding in water promptly obtains a kind of direct methanol fuel cell proton exchange membrane.
With the H of above-mentioned proton exchange membrane at 1M
2SO
4Soaked 24 hours in the aqueous solution, use deionized water wash again to remove residual H in the striping
2SO
4, be immersed in then in the deionized water preserve stand-by.
The direct methanol fuel cell of present embodiment preparation reaches 1.202 * 10 with the proton conductivity of proton exchange membrane 25 ℃ the time
-2S/cm, methanol crossover coefficient are 6.06 * 10
-8Cm
2/ s.
As shown in Figure 1, along with the rising of temperature, the swellbility of all films in water all increases thereupon, and pure SPEEK film is after temperature is higher than 50 ℃, and its swellbility sharply becomes big with the increase of temperature, and SPEEK/SiO
2The swellbility of/PWA (85/5/10) composite membrane is less with variation of temperature, visible SPEEK/SiO
2/ PWA (85/5/10) composite membrane is difficult for swelling under higher temperature; As shown in Figure 2, SPEEK matrix and SiO
2Boundary between the particle thickens, and SiO
2Form cross-linked network structure with the SPEEK matrix, PWA is dispersed in the cancellated grid with the granule state, and the dispersive property of visible particles in polymeric matrix is very good; As shown in Figure 3, SiO
2With the introducing of PWA the proton conductivity of film is raise, and the proton conductivity of all films all increase along with the rising of temperature, below 85 ℃ the time, SPEEK/SiO
2The proton conductivity of/PWA (85/5/10) composite membrane is lower than the Nafion117 film slightly, but all reaches 10
-2The order of magnitude of S/cm, when temperature is higher than after 85 ℃, the proton conductivity of composite membrane is higher than the proton conductivity of Nafion117 film; As shown in Figure 4, SiO
2With the introducing of PWA the methanol permeability of composite membrane is reduced, and be significantly less than the methanol permeability of Nafon117 film.
(1) 6 gram polyether-ether-ketone pellets being dissolved in 300 gram weight percent concentrations is in 98% the concentrated sulfuric acid, 60 ℃ of following vigorous stirring, continue sulfonation after 12 hours, reactant poured in the frozen water dilute, making the frozen water volume is 6 times of reaction solution, with the reacting liquid filtering taking precipitate of dilution, be neutral back 60 ℃ of following vacuumizes 24 hours with distilled water cyclic washing sediment until the aqueous solution, obtain sulfonated polyether-ether-ketone (SPEEK);
(2) 6 gram SPEEK are dissolved in the anhydrous N of 44 grams, in the N-dimethyl pyrrolidone (NMP), are made into 12wt.% solution.Add 0.57 gram N again, N '-carbonyl dimidazoles (CDI) makes on CDI and the SPEEK-SO
3The mol ratio of H was 1: 3.5,60 ℃ of stirring reactions 1 hour.Add 0.91 gram γ-(2,3-encircles third oxygen) propyl trimethoxy silicane (GPTS) again, the mol ratio of GPTS and CDI is 1: 1, and obtains the sulfonated polyether-ether-ketone reactant liquor in 3 hours at 60 ℃ of stirring reactions.
(3) will be 1: 8 silicon dioxide (SiO with the mass ratio of sulfonated polyether-ether-ketone
2) 0.75 gram carries out the ultrasonic wave dispersion treatment, join then in the above-mentioned sulfonated polyether-ether-ketone reactant liquor, stirred 7 hours down at 65 ℃, to be 1: 8 alpha zirconium phosphate (α-ZrP) join in the above-mentioned solution after the 0.75 gram ultrasonic wave dispersion treatment again with the mass ratio of sulfonated polyether-ether-ketone, stirred 9 hours down at 65 ℃, having obtained sulfonated polyether-ether-ketone/silicon dioxide/alpha zirconium phosphate proportioning like this is 80: 10: 10 mixed solution;
(4) with mixture solution film forming on the mould that glass plate and polyester film surrounded of above-mentioned sulfonated polyether-ether-ketone/silicon dioxide/alpha zirconium phosphate, drying is 24 hours under 60 ℃, after being cooled to room temperature, demoulding in water promptly obtains a kind of direct methanol fuel cell proton exchange membrane.
With the above-mentioned a kind of direct methanol fuel cell H of proton exchange membrane at 1M
2SO
4Soaked 24 hours in the aqueous solution, use deionized water wash again to remove residual H in the striping
2SO
4, be immersed in then in the deionized water preserve stand-by.
The proton conductivity of the direct methanol fuel cell of present embodiment preparation during with 45 ℃ of proton exchange membrane reaches 1.844 * 10
-2S/cm, methanol crossover coefficient are 9.65 * 10
-8Cm2/s.
(1) 4 gram polyether-ether-ketone pellets being dissolved in 160 gram weight percent concentrations is in 98% the concentrated sulfuric acid, 50 ℃ of following vigorous stirring, continue sulfonation after 18 hours, reactant poured in the frozen water dilute, making the frozen water volume is 8 times of reaction solution, with the reacting liquid filtering taking precipitate of dilution, be neutral back 60 ℃ of following vacuumizes 24 hours with distilled water cyclic washing sediment until the aqueous solution, obtain sulfonated polyether-ether-ketone (SPEEK);
(2) 4g SPEEK is dissolved in the anhydrous N of 22.7g, in the dinethylformamide (DMF), is made into 15wt.% solution.Add 0.54 gram N again, N '-carbonyl dimidazoles (CDI), on CDI and the SPEEK-SO
3The mol ratio of H was 1: 2.5,60 ℃ of stirring reactions 2.5 hours.Add 0.74 gram gamma-aminopropyl-triethoxy-silane again, the mol ratio of gamma-aminopropyl-triethoxy-silane and CDI is 1: 1, and obtains the sulfonated polyether-ether-ketone reactant liquor in 4 hours at 60 ℃ of stirring reactions.
(3) will be 1: 7.5 alundum (Al (Al with the sulfonated polyether-ether-ketone weight ratio
2O
3) 0.533 gram carries out the ultrasonic wave dispersion treatment, join then in the above-mentioned sulfonated polyether-ether-ketone reactant liquor, stirred 12 hours down at 50 ℃, to be that 1: 5 silico-tungstic acid (SWA) 0.8 gram ultrasonic wave disperses reprocessing to join in the above-mentioned solution with the sulfonated polyether-ether-ketone weight ratio again, stirred 14 hours down at 50 ℃, obtaining sulfonated polyether-ether-ketone/alundum (Al/silico-tungstic acid proportioning like this is 75: 10: 15 mixed solution;
(4) with mixture solution film forming on the mould that glass plate and polyester film surrounded of sulfonated polyether-ether-ketone/alundum (Al/silico-tungstic acid, drying is 32 hours under 55 ℃, after being cooled to room temperature, demoulding in water promptly obtains a kind of direct methanol fuel cell proton exchange membrane.
With the above-mentioned a kind of direct methanol fuel cell H of proton exchange membrane at 1M
2SO
4Soaked 24 hours in the aqueous solution, use deionized water wash again to remove residual H in the striping
2SO
4, be immersed in then in the deionized water preserve stand-by.
The direct methanol fuel cell of present embodiment preparation reaches 3.365 * 10 with the proton conductivity of proton exchange membrane 65 ℃ the time
-2S/cm, methanol crossover coefficient are 6.23 * 10
-7Cm
2/ s.
(1) 5 gram polyether-ether-ketone pellets being dissolved in 350 gram weight percent concentrations is in 95% the concentrated sulfuric acid, 55 ℃ of following vigorous stirring, continue sulfonation after 20 hours, reactant poured in the frozen water dilute, making the frozen water volume is 6 times of reaction solution, with the reacting liquid filtering taking precipitate of dilution, be neutral back 60 ℃ of following vacuumizes 24 hours with distilled water cyclic washing sediment until the aqueous solution, obtain sulfonated polyether-ether-ketone (SPEEK);
(2) 5 gram SPEEK are dissolved in the anhydrous N of 30.7 grams, in the N-dimethylacetylamide (DMAc), are made into 14wt.% solution.Add 0.56 gram N again, N '-carbonyl dimidazoles (CDI) makes on CDI and the SPEEK-SO
3The mol ratio of H was 1: 3,60 ℃ of stirring reactions 3 hours.Add 0.71 gram N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane again, the mol ratio of N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane and CDI is 1: 1, and obtains the sulfonated polyether-ether-ketone reactant liquor in 2.5 hours at 60 ℃ of following stirring reactions;
(3) will be 1: 5 titanium dioxide (TiO with the sulfonated polyether-ether-ketone weight ratio
2) 1 gram carries out the ultrasonic wave dispersion treatment, joins then in the above-mentioned sulfonated polyether-ether-ketone reactant liquor, stirred 6 hours down at 75 ℃, will be 1: 7.5 orthophosphoric acid boron (BPO again with the sulfonated polyether-ether-ketone weight ratio
4) 0.67 gram ultrasonic wave disperses reprocessing to join in the above-mentioned solution, stirs 8 hours down at 75 ℃, obtaining sulfonated polyether-ether-ketone/titanium dioxide/orthophosphoric acid boron proportioning like this is 75: 15: 10 mixed solution;
(4) with mixture solution film forming on the mould that glass plate and polyester film surrounded of sulfonated polyether-ether-ketone/titanium dioxide/orthophosphoric acid boron, drying is 24 hours under 65 ℃, after being cooled to room temperature, demoulding in water promptly obtains a kind of direct methanol fuel cell proton exchange membrane.
With the above-mentioned a kind of direct methanol fuel cell H of proton exchange membrane at 1M
2SO
4Soaked 24 hours in the aqueous solution, use deionized water wash again to remove residual H in the striping
2SO
4, be immersed in then in the deionized water preserve stand-by.
The direct methanol fuel cell of present embodiment preparation reaches 2.846 * 10 with the proton conductivity of proton exchange membrane 75 ℃ the time
-2S/cm, methanol crossover coefficient are 5.32 * 10
-7Cm
2/ s.
Embodiment 5
(1) 8 gram polyether-ether-ketone pellets being dissolved in 600 gram weight percent concentrations is in 97% the concentrated sulfuric acid, 25 ℃ of following vigorous stirring, continue sulfonation after 50 hours, reactant poured in the frozen water dilute, making the frozen water volume is 8 times of reaction solution, with the reacting liquid filtering taking precipitate of dilution, be neutral back 60 ℃ of following vacuumizes 24 hours with distilled water cyclic washing sediment until the aqueous solution, obtain sulfonated polyether-ether-ketone (SPEEK);
(2) 8 gram SPEEK are dissolved in the anhydrous N of 53.5 grams, in the dinethylformamide (DMF), are made into 13wt.% solution.Add 1.35 gram N again, N '-carbonyl dimidazoles (CDI) makes on CDI and the SPEEK-SO
3The mol ratio of H was 1: 2,60 ℃ of stirring reactions 1.5 hours.Add 1.87 gram aminopropyltriethoxywerene werene (AS) again, aminopropyltriethoxywerene werene (AS) is 1: 1 with the mol ratio of CDI, and obtains the sulfonated polyether-ether-ketone reactant liquor in 1.5 hours at 60 ℃ of following stirring reactions;
(3) will be 1: 8.5 zirconium dioxide (ZrO with the sulfonated polyether-ether-ketone weight ratio
2) 0.94 gram carries out the ultrasonic wave dispersion treatment, joins then in the above-mentioned sulfonated polyether-ether-ketone reactant liquor, stirred 10 hours down at 80 ℃, will be 1: 17 basic zirconium phosphate (Zr (HPO again with the sulfonated polyether-ether-ketone weight ratio
4) 2) 0.47 gram ultrasonic wave disperses reprocessing to join in the above-mentioned solution, stirs 10 hours down at 80 ℃, obtaining sulfonated polyether-ether-ketone/zirconium dioxide/basic zirconium phosphate proportioning like this is 85: 10: 5 mixed solution;
(4) with mixture solution film forming on the mould that glass plate and polyester film surrounded of sulfonated polyether-ether-ketone/zirconium dioxide/basic zirconium phosphate, drying is 32 hours under 55 ℃, after being cooled to room temperature, demoulding in water promptly obtains a kind of direct methanol fuel cell proton exchange membrane.
With the above-mentioned a kind of direct methanol fuel cell H of proton exchange membrane at 1M
2SO
4Soaked 24 hours in the aqueous solution, use deionized water wash again to remove residual H in the striping
2SO
4, be immersed in then in the deionized water preserve stand-by.
The direct methanol fuel cell of present embodiment preparation reaches 4.238 * 10 with the proton conductivity of proton exchange membrane 80 ℃ the time
-2S/cm, methanol crossover coefficient are 9.56 * 10
-7Cm
2/ s.
(1) 10 gram polyether-ether-ketone pellets being dissolved in 350 gram weight percent concentrations is in 96% the concentrated sulfuric acid, 60 ℃ of following vigorous stirring, continue sulfonation after 10 hours, reactant poured in the frozen water dilute, making the frozen water volume is 7 times of reaction solution, with the reacting liquid filtering taking precipitate of dilution, be neutral back 60 ℃ of following vacuumizes 24 hours with distilled water cyclic washing sediment until the aqueous solution, obtain sulfonated polyether-ether-ketone (SPEEK);
(2) 10 gram SPEEK are dissolved in the anhydrous N of 90 grams, in the N-dimethylacetylamide (DMAc), are made into 10wt.% solution.Add 0.96 gram N again, N '-carbonyl dimidazoles (CDI) makes on CDI and the SPEEK-SO
3The mol ratio of H was 1: 3.5,60 ℃ of stirring reactions 2 hours.Add 1.31 gram gamma-aminopropyl-triethoxy-silanes again, the mol ratio of gamma-aminopropyl-triethoxy-silane and CDI is 1: 1 and obtained the sulfonated polyether-ether-ketone reactant liquor in 3.5 hours at 60 ℃ of following stirring reactions;
(3) with the sulfonated polyether-ether-ketone weight ratio be 5 hydrochloric acid of adding in 1: 7 1.42 grams positive silicic acid orthocarbonates (TPOS), and it is carried out the ultrasonic wave dispersion treatment, join then in the above-mentioned sulfonated polyether-ether-ketone reactant liquor, stirred 9 hours down at 70 ℃, to be that 1: 3.5 silico-tungstic acid (SWA) 2.84 gram ultrasonic waves disperse reprocessings to join in the above-mentioned solution with the sulfonated polyether-ether-ketone weight ratio again, stirred 11 hours down at 70 ℃, obtaining sulfonated polyether-ether-ketone/silica/silicon wolframic acid proportioning like this is 70: 10: 20 mixed solution;
(4) with mixture solution film forming on the mould that glass plate and polyester film surrounded of sulfonated polyether-ether-ketone/silica/silicon wolframic acid, drying is 26 hours under 65 ℃, after being cooled to room temperature, demoulding in water promptly obtains a kind of direct methanol fuel cell proton exchange membrane.
With the above-mentioned a kind of direct methanol fuel cell H of proton exchange membrane at 1M
2SO
4Soaked 24 hours in the aqueous solution, use deionized water wash again to remove residual H in the striping
2SO
4, be immersed in then in the deionized water preserve stand-by.
The direct methanol fuel cell of present embodiment preparation reaches 1.393 * 10 with the proton conductivity of proton exchange membrane 20 ℃ the time
-2S/cm, methanol crossover coefficient are 3.14 * 10
-8Cm
2/ s.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. the preparation method of a direct methanol fuel cell usefulness proton exchange membrane is characterized in that comprising the steps:
(1) calculates by weight, it is to carry out sulfonating reaction in 95～98% the concentrated sulfuric acid that 1 part of polyether-ether-ketone is added to 35～75 parts of weight percent concentration, then taking precipitate is filtered in reactant liquor dilution back, water is washed till the aqueous solution with sediment and is neutral back drying and obtains sulfonated polyether-ether-ketone;
(2) sulfonated polyether-ether-ketone is dissolved in the organic solvent, be made into weight percent concentration and be 10～15% sulfonated polyether-ether-ketone solution, add N, N '-carbonyl dimidazoles (CDI), the N that is added, the mol ratio of sulfonate radical is 1: 2～4 in N '-carbonyl dimidazoles and the sulfonated polyether-ether-ketone; Stir and add the coupling agent stirring reaction after 1～3 hour again and obtained the sulfonated polyether-ether-ketone reactant liquor in 1.5～4 hours, coupling agent that is added and N, the mol ratio of N '-carbonyl dimidazoles is 1: 1;
(3) will be that 1: 5～17 inorganic crosslinking agent joins in the above-mentioned sulfonated polyether-ether-ketone reactant liquor with the sulfonated polyether-ether-ketone weight ratio, reacted 6～12 hours down at 50～80 ℃, adding is 1: 3.5～17 proton conductors with the sulfonated polyether-ether-ketone weight ratio then, continues to obtain after reacting 8～14 hours under this temperature the mixed solution of sulfonated polyether-ether-ketone/inorganic crosslinking agent/proton conductor;
(4) with the mixture solution film forming of sulfonated polyether-ether-ketone/inorganic crosslinking agent/proton conductor, drying, demoulding promptly obtains described direct methanol fuel cell proton exchange membrane.
2. the direct methanol fuel cell according to claim 1 preparation method of proton exchange membrane is characterized in that: the sulfonating reaction condition is 25～60 ℃ of following sulfonating reactions 8～50 hours in the described step (1).
3. the direct methanol fuel cell according to claim 1 preparation method of proton exchange membrane is characterized in that: organic solvent comprises N, N-dimethylacetylamide, N, dinethylformamide or N-crassitude in the described step (2).
4. the direct methanol fuel cell according to claim 1 preparation method of proton exchange membrane, it is characterized in that: coupling agent is aminopropyltriethoxywerene werene, γ-(2,3-encircles third oxygen) propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane or N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane in the described step (2).
5. the direct methanol fuel cell according to claim 1 preparation method of proton exchange membrane is characterized in that: inorganic crosslinking agent comprises silicon dioxide, titanium dioxide, alundum (Al, zirconium dioxide or silica-based esterification products in the described step (3).
6. the direct methanol fuel cell according to claim 1 preparation method of proton exchange membrane is characterized in that: proton conductor comprises phosphotungstic acid, silico-tungstic acid, basic zirconium phosphate or orthophosphoric acid boron in the described step (3).
7. the direct methanol fuel cell according to claim 1 preparation method of proton exchange membrane is characterized in that: inorganic crosslinking agent and proton conductor carried out the ultrasonic wave dispersion treatment earlier in the described step (3) before adding.
8. direct methanol fuel cell according to claim 1 is characterized in that with the preparation method of proton exchange membrane: in the described step (4) dry for 55～65 ℃ dry 24～32 hours down.
9. any prepared direct methanol fuel cell proton exchange membrane of claim 1～9, it is characterized in that: its proton conductivity at 20～80 ℃ is 1.202 * 10
-2～4.238 * 10
-2S/cm, methanol crossover coefficient are 3.14 * 10
-8～9.56 * 10
-7Cm
2/ s.
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