CN102108132B - Preparation method and application of sulfonated polyether-ether-ketone-carboxylated titanium dioxide hybrid membrane - Google Patents
Preparation method and application of sulfonated polyether-ether-ketone-carboxylated titanium dioxide hybrid membrane Download PDFInfo
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- CN102108132B CN102108132B CN201110020967A CN201110020967A CN102108132B CN 102108132 B CN102108132 B CN 102108132B CN 201110020967 A CN201110020967 A CN 201110020967A CN 201110020967 A CN201110020967 A CN 201110020967A CN 102108132 B CN102108132 B CN 102108132B
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Abstract
The invention discloses a preparation method and application of a sulfonated polyether-ether-ketone-carboxylated titanium dioxide hybrid membrane. The preparation method comprises the following steps of: preparing sulfonated polyether-ether-ketone and solution of the sulfonated polyether-ether-ketone; preparing carboxylated titanium dioxide sol; mixing the carboxylated titanium dioxide sol and the solution of the sulfonated polyether-ether-ketone to perform condensation polymerization to form membrane casting solution; after standing, filtering and de-foaming the membrane casting solution, curtain coating, drying and annealing the membrane casting solution to form a membrane; and acidizing and drying the membrane to obtain the sulfonated polyether-ether-ketone-carboxylated titanium dioxide hybrid membrane. The hybrid membrane serves as a direct methanol fuel cell proton exchange membrane. The hybrid membrane has the advantages that: the preparation method is simple; nano inorganic titanium dioxide particles are uniformly distributed in the prepared membrane; a carboxyl group effectively improves the performance of the membrane; and the hybrid membrane has relatively low methanol permeability and relatively high proton conductivity.
Description
Technical field
The present invention relates to a kind of sulfonated polyether-ether-ketone (SPEEK)-carboxylic acid oxide/titanium dioxide (TiO
2-COOH) the preparation and the application thereof of hybridized film belongs to hybrid inorganic-organic hybridized film technology.
Background technology
Fuel cell is a kind of new chemical energy, and it is a kind of without burning, directly changes the chemical energy of fuel the device of electric energy into the mode of electrochemical reaction, has the generating efficiency height, is applicable to pluralities of fuel and advantages of environment protection.Wherein, Directly DMFC is to be fuel with methyl alcohol; Compare with other fuel cells have that but normal temperature starts fast, energy density high, fuel cheaply abundantly is prone to store, simple in structure, outstanding advantage such as cost is low, is described as 21 century novel portable power supply the most likely.PEM is one of DMFC key part, and present business-like PEM is mainly the Nafion series membranes of perfluoro sulfonic acid membrane such as Dupond company.But this type of film exists serious methanol crossover phenomenon when being used for DMFC.Research shows that when methanol concentration was 1mol/L, the methanol crossover amount can be up to 40%; Battery circuit density is 150mA/cm
2The time, the methanol crossover current density reaches 80mA/cm
2In addition, the perfluoro sulfonic acid membrane (600～1200$/m that costs an arm and a leg
2), this has all limited DMFC technology popularization and commercial applications greatly.Therefore, features good methanol diffusion resistance, the high and low cost of proton conductivity the preparation of novel proton exchange membranes become the focus of current research.Hybrid organic-inorganic film has the methanol crossover of inhibition and improves advantages such as film machinery and thermostability thereof because of it; And will have the inorganic particle of leading the proton ability be filled into can play in the film resistance pure and mild raising proton conduction dual function; Wherein the original position sol-gel method can be that the polycondensation process of inorganic precursor provides nano level space constraint through macromolecule member material; Thereby reach control inorganic particle particle diameter and stable nanoparticles and prevent that it from the effect of reuniting taking place, and obtains the finely dispersed hybrid organic-inorganic film of inorganic component.Up to the present, original position generates the PEM that sulfonated polyether-ether-ketone (SPEEK)-carboxylic acid oxide/titanium dioxide hybridized film film is used for DMFC and does not see bibliographical information.
Summary of the invention
The object of the invention is in preparation and application thereof that a kind of sulfonated polyether-ether-ketone-carboxylic acid oxide/titanium dioxide hybridized film is provided.This preparing method's process is simple, and made hybridized film is used for DMFC, has the pure and mild proton conduction performance of higher resistance.
The present invention realizes that through following technical scheme the preparation method of a kind of sulfonated polyether-ether-ketone-carboxylic acid oxide/titanium dioxide hybridized film is characterized in that may further comprise the steps:
1. the exsiccant polyetheretherketone being dissolved in mass concentration is in 98% the sulfuric acid; Be mixed with mass concentration and be 14～18% polyetheretherketone sulphuric acid soln, the polyetheretherketone sulphuric acid soln is 45～50 ℃ of temperature and stir down and carry out sulfonation reaction 6～8h, with obtaining throw out in the thick reactant adding deionized water; Throw out is again through deionized water wash; Wash to liquid pH be 7, through dry, obtaining sulfonation degree is 55～70% sulfonated polyether-ether-ketones again;
2. in room temperature and under stirring, be that 55～70% sulfonated polyether-ether-ketones are dissolved into N with sulfonation degree, in the dinethylformamide, being mixed with mass concentration is 10～14% sulfonated polyether-ether-ketone solution;
3. under the room temperature; With mass percent is that 10～50% butyl(tetra)titanate and methyl ethyl diketone are 1: 1.5～2.5 to carry out joining among the DMF behind the chelating in molar ratio; And stir 3～4h, and obtain the butyl(tetra)titanate solution behind the methyl ethyl diketone chelating, be to add deionized water in 1: 4～8 the butyl(tetra)titanate solution behind the methyl ethyl diketone chelating according to the mol ratio of butyl(tetra)titanate and deionized water then; And according to butyl(tetra)titanate and 3; The mass ratio of 4-dihydroxy-benzene propionic acid is 1: 0.045～0.050 adding 3, and 4-dihydroxy-benzene propionic acid obtains maroon carboxylic acid oxide/titanium dioxide sol solution.
4. the carboxylic acid oxide/titanium dioxide sol solution that step 3 is obtained joins in the sulfonated polyether-ether-ketone solution that step 2 obtains slowly; And under room temperature, stir 1～2h, leave standstill, copper mesh filters deaeration and obtain film-casting liquid, and the gained film-casting liquid is poured on curtain coating on the clean sheet glass; And place baking oven dry; After temperature was 110～120 ℃ of thermal treatment 2～3h, anneal 2～3h under the room temperature took off and places 2M sulfuric acid to handle 10～12h film then; Afterwards with deionized water rinsing till washings is neutrality, wet film is obtained sulfonated polyether-ether-ketone/carboxylic acid oxide/titanium dioxide hybridized film 50～60 ℃ of following vacuum-dryings.
The sulfonated polyether-ether-ketone of method for preparing-carboxylic acid oxide/titanium dioxide hybridized film, as the PEM of DMFC, its proton conductivity is 0.626 * 10
-2～0.925 * 10
-2S/cm, methanol permeability are 1.776 * 10
-6～1.249 * 10
-6Cm
2/ s.
The invention has the advantages that: prepare hybridized film through original position synthetic method; Not only process is succinct; And polymeric matrix (SPEEK) provides nano level space constraint for the polycondensation process of reactant (TBT); Prevent that it from the effect of reuniting taking place thereby reach control inorganic particle particle diameter and stable nanoparticles, so obtain the finely dispersed hybrid organic-inorganic film of inorganic component.In addition, this method is also modified inorganic component through the phenylpropionic acid of band carboxylate radical and is improved film properties.Prepared SPEEK/TiO
2-COOH hybridized film not only has lower methanol permeability in the 2M methanol aqueous solution, but also shows suitable proton conductivity, can be used as the DMFC PEM.
Description of drawings
Fig. 1 is the profile scanning electron micrograph of the pure sulfonated polyether-ether-ketone film of comparative example's preparation.
Fig. 2 is the profile scanning electron micrograph of the sulfonated polyether-ether-ketone-carboxylic acid oxide/titanium dioxide hybridized film of the embodiment of the invention 3 preparations.
Embodiment
Embodiment 1
Take by weighing 0.7g sulfonated polyether-ether-ketone (SPEEK) and be dissolved into 5g N, in the dinethylformamide (DMF), at room temperature stir the 12h dissolving and obtain the SPEEK film-casting liquid.Under the room temperature, with the 0.07g butyl(tetra)titanate with join among the 2g DMF after the 0.041g methyl ethyl diketone mixes, and stir 3h, the water that slowly adds the pH=1 of 0.0037g subsequently continues to stir the TiO 2 sol that 10h obtains yellow transparent.Take by weighing then and get 3 of 0.0033g, 4-dihydroxy phenyl propionic acid joins in the TiO 2 sol of gained, obtains the solution of maroon.Mixed slowly being incorporated under the room temperature of above-mentioned two parts of solution that obtain stirred 1h; The filtering and standing deaeration; The gained film-casting liquid is poured on curtain coating on the clean sheet glass; And place baking oven dry 12h under 60 ℃ earlier, be warming up to 80 ℃ of dry 10h then, after take off and place 2M sulfuric acid to handle 12h film after 120 ℃ of anneal; Afterwards with deionized water wash repeatedly remove residual acid after, wet film is obtained sulfonated polyether-ether-ketone hybridized film/carboxylic acid oxide/titanium dioxide hybridized film (film 1.SPEEK/TiO at 60 ℃ of vacuum-drying 12h
2-COOH-10).
Embodiment 2
Take by weighing 0.7g sulfonated polyether-ether-ketone (SPEEK) and be dissolved into 5g N, in the dinethylformamide (DMF), at room temperature stir the 12h dissolving and obtain the SPEEK film-casting liquid.Under the room temperature, with the 0.14g butyl(tetra)titanate with join among the 2g DMF after the 0.082g methyl ethyl diketone mixes, and stir 3h, the water that slowly adds the pH=1 of 0.059g subsequently continues to stir the TiO 2 sol that 10h obtains yellow transparent.Take by weighing 3 of 0.0066g then, 4-dihydroxy phenyl propionic acid joins in the TiO 2 sol of gained, obtains the solution of maroon.Mixed slowly being incorporated under the room temperature of above-mentioned two parts of solution that obtain stirred 1h; The filtering and standing deaeration; The gained film-casting liquid is poured on curtain coating on the clean sheet glass; And place baking oven dry 12h under 60 ℃ earlier, be warming up to 80 ℃ of dry 10h then, after take off and place 2M sulfuric acid to handle 12h film after 120 ℃ of anneal; Afterwards with deionized water wash repeatedly remove residual acid after, wet film is obtained sulfonated polyether-ether-ketone hybridized film/carboxylic acid oxide/titanium dioxide hybridized film (film 2.SPEEK/TiO at 60 ℃ of vacuum-drying 12h
2-COOH-20).
Embodiment 3
Take by weighing 0.7g sulfonated polyether-ether-ketone (SPEEK) and be dissolved into 5g N, in the dinethylformamide (DMF), at room temperature stir the 12h dissolving and obtain the SPEEK film-casting liquid.Under the room temperature, with the 0.21g butyl(tetra)titanate with join among the 2g DMF after the 0.123g methyl ethyl diketone mixes, and stir 3h, the water that slowly adds the pH=1 of 0.089g subsequently continues to stir the TiO 2 sol that 10h obtains yellow transparent.Take by weighing 3 of 0.0099g then, 4-dihydroxy phenyl propionic acid joins in the TiO 2 sol of gained, obtains the solution of maroon.Mixed slowly being incorporated under the room temperature of above-mentioned two parts of solution that obtain stirred 1h; The filtering and standing deaeration; The gained film-casting liquid is poured on curtain coating on the clean sheet glass; And place baking oven dry 12h under 60 ℃ earlier, be warming up to 80 ℃ of dry 10h then, after take off and place 2M sulfuric acid to handle 12h film after 120 ℃ of anneal; Afterwards with deionized water wash repeatedly remove residual acid after, wet film is obtained sulfonated polyether-ether-ketone hybridized film/carboxylic acid oxide/titanium dioxide hybridized film (film 3.SPEEK/TiO at 60 ℃ of vacuum-drying 12h
2-COOH-30).
Embodiment 4
Take by weighing 0.7g sulfonated polyether-ether-ketone (SPEEK) and be dissolved into 5gN, in the dinethylformamide (DMF), at room temperature stir the 12h dissolving and obtain the SPEEK film-casting liquid.Under the room temperature, with the 0.28g butyl(tetra)titanate with join among the 2g DMF after the 0.165g methyl ethyl diketone mixes, and stir 3h, the water that slowly adds the pH=1 of 0.0118g subsequently continues to stir the TiO 2 sol that 10h obtains yellow transparent.Take by weighing 3 of 0.0131g then, 4-dihydroxy phenyl propionic acid joins in the TiO 2 sol of gained, obtains the solution of maroon.Mixed slowly being incorporated under the room temperature of above-mentioned two parts of solution that obtain stirred 1h; The filtering and standing deaeration; The gained film-casting liquid is poured on curtain coating on the clean sheet glass; And place baking oven dry 12h under 60 ℃ earlier, be warming up to 80 ℃ of dry 10h then, after take off and place 2M sulfuric acid to handle 12h film after 120 ℃ of anneal; Afterwards with deionized water wash repeatedly remove residual acid after, wet film is obtained sulfonated polyether-ether-ketone hybridized film/carboxylic acid oxide/titanium dioxide hybridized film (film 4.SPEEK/TiO at 60 ℃ of vacuum-drying 12h
2-COOH-40).
Embodiment 5
Take by weighing 0.7g sulfonated polyether-ether-ketone (SPEEK) and be dissolved into 5g N, in the dinethylformamide (DMF), at room temperature stir the 12h dissolving and obtain the SPEEK film-casting liquid.Under the room temperature, with the 0.35g butyl(tetra)titanate with join among the 2g DMF after the 0.206g methyl ethyl diketone mixes, and stir 3h, the water that slowly adds the pH=1 of 0.148g subsequently continues to stir the TiO 2 sol that 10h obtains yellow transparent.Take by weighing 3 of 0.0164g then, 4-dihydroxy phenyl propionic acid joins in the TiO 2 sol of gained, obtains the solution of maroon.Mixed slowly being incorporated under the room temperature of above-mentioned two parts of solution that obtain stirred 1h; The filtering and standing deaeration; The gained film-casting liquid is poured on curtain coating on the clean sheet glass; And place baking oven dry 12h under 60 ℃ earlier, be warming up to 80 ℃ of dry 10h then, after take off and place 2M HCl to handle 12h film after 120 ℃ of anneal; Afterwards with deionized water wash repeatedly remove residual acid after, wet film is obtained sulfonated polyether-ether-ketone hybridized film/carboxylic acid oxide/titanium dioxide hybridized film (film 5.SPEEK/TiO at 60 ℃ of vacuum-drying 12h
2-COOH-50).
The comparative example
Take by weighing the 0.7g sulfonated polyether-ether-ketone and be dissolved into 7g N; In the dinethylformamide, at room temperature stir the 12h dissolving and obtain SPEEK film-casting liquid, filtering and standing deaeration; The gained film-casting liquid is poured on curtain coating on the clean sheet glass; And place baking oven dry 12h under 60 ℃ earlier, be warming up to 80 ℃ of dry 10h then, after take off and place 2M HCl to handle 12h film after 120 ℃ of anneal; Afterwards with deionized water wash repeatedly remove residual acid after, wet film is obtained pure sulfonated polyether-ether-ketone film (film 6.SPEEK) at 60 ℃ of vacuum-drying 12h.
Table 1 is depicted as the prepared film 1 of embodiment, film 2, film 3, film 4, film 5 and the methanol permeability of the prepared film 6 of comparative example and the result of proton conductivity.
Claims (2)
1. the preparation method of sulfonated polyether-ether-ketone-carboxylic acid oxide/titanium dioxide hybridized film is characterized in that may further comprise the steps:
1) the exsiccant polyetheretherketone being dissolved in mass concentration is in 98% the sulfuric acid; Be mixed with mass concentration and be 14～18% polyetheretherketone sulphuric acid soln, the polyetheretherketone sulphuric acid soln is 45～50 ℃ of temperature and stir down and carry out sulfonation reaction 6～8h, with obtaining throw out in the thick reactant adding deionized water; Throw out is again through deionized water wash; Wash to liquid pH be 7, through dry, obtaining sulfonation degree is 55～70% sulfonated polyether-ether-ketones again;
2) in room temperature and under stirring, be that 55～70% sulfonated polyether-ether-ketones are dissolved into N with sulfonation degree, in the dinethylformamide, being mixed with mass concentration is 10～14% sulfonated polyether-ether-ketone solution;
3) under the room temperature; With mass percent is that 10～50% butyl(tetra)titanate and methyl ethyl diketone are 1: 1.5～2.5 to carry out joining N behind the chelating in molar ratio, in the dinethylformamide, and stirs 3～4h; Obtain the butyl(tetra)titanate solution behind the methyl ethyl diketone chelating; Be to add deionized water in 1: 4～8 the butyl(tetra)titanate solution behind the methyl ethyl diketone chelating according to the mol ratio of butyl(tetra)titanate and deionized water then, and according to butyl(tetra)titanate and 3, the mass ratio of 4-dihydroxy-benzene propionic acid is 1: 0.045～0.050 to add 3; 4-dihydroxy-benzene propionic acid obtains maroon carboxylic acid oxide/titanium dioxide sol solution;
4) the carboxylic acid oxide/titanium dioxide sol solution that step 3) is obtained joins step 2 slowly) in the sulfonated polyether-ether-ketone solution that obtains; And under room temperature, stir 1～2h, leave standstill, copper mesh filters deaeration and obtain film-casting liquid, and the gained film-casting liquid is poured on curtain coating on the clean sheet glass; And place baking oven dry; After temperature was 110～120 ℃ of thermal treatment 2～3h, anneal 2～3h under the room temperature took off and places 2M sulfuric acid to handle 10～12h film then; Afterwards with deionized water rinsing till washings is neutrality, be that 50～60 ℃ of following vacuum-dryings obtain sulfonated polyether-ether-ketone/carboxylic acid oxide/titanium dioxide hybridized film with wet film in temperature.
2. application by the sulfonated polyether-ether-ketone-carboxylic acid oxide/titanium dioxide hybridized film of the said method preparation of claim 1, as the PEM of DMFC, its proton conductivity is 0.626 * 10
-2～0.925 * 10
-2S/cm, methanol permeability are 1.776 * 10
-6～1.249 * 10
-6Cm
2/ s.
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| CN102974230B (en) * | 2012-12-04 | 2014-10-29 | 天津大学 | Chitosan/titanium dioxide ultrathin hybrid film, and preparation method and application thereof |
| CN103304979B (en) * | 2013-07-26 | 2015-07-01 | 天津大学 | Phosphorylation titanium dioxide hollow sphere-filled sulfonated polyether ether ketone film as well as preparation and application |
| CN103554831A (en) * | 2013-10-29 | 2014-02-05 | 天津大学 | Sulfonated polyetheretherketone/amino-functionalized TiO2 hybrid membrane, as well as preparation and applications of hybrid membrane |
| CN103865231B (en) * | 2014-03-13 | 2015-09-16 | 天津大学 | Sulfonated polyether-ether-ketone-original position phosphorylation titania hybrid film and Synthesis and applications |
| CN104028121B (en) * | 2014-06-18 | 2016-08-24 | 天津大学 | Sulfonated polyether-ether-ketone-amido modified titanium nanotube hybridized film and preparation and application |
| CN104209023B (en) * | 2014-08-27 | 2016-08-17 | 天津大学 | Sulfonated polyether-ether-ketone-sulfonation silicon dioxide microsphere hybridized film and preparation and application |
| CN107785521B (en) * | 2016-08-29 | 2021-03-26 | 比亚迪股份有限公司 | Battery diaphragm, lithium ion battery and preparation method thereof |
| CN106711482B (en) * | 2017-01-18 | 2019-03-29 | 吉林大学 | Crystalline polymer three-dimensional network enhances sulfonated-polyethercompositetone-based compositetone-based ion-exchange membrane and preparation method thereof |
| CN109950596A (en) * | 2019-04-03 | 2019-06-28 | 山东星火科学技术研究院 | A kind of three-dimensional polyether-ether-ketone network membrane material and preparation method thereof |
| CN109971012A (en) * | 2019-04-03 | 2019-07-05 | 山东星火科学技术研究院 | A kind of preparation method of inorganic nano-particle doping vario-property sulfonated polyether-ether-ketone film |
| CN117199466B (en) * | 2023-11-07 | 2024-03-12 | 杭州德海艾科能源科技有限公司 | High-conductivity composite membrane for vanadium redox flow battery and preparation method thereof |
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| CN101531765A (en) * | 2009-04-10 | 2009-09-16 | 天津大学 | Method for preparing sulfonated polymer films |
| CN201326018Y (en) * | 2008-12-10 | 2009-10-14 | 天津大学 | Pressure type water electrolyser |
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| CN201326018Y (en) * | 2008-12-10 | 2009-10-14 | 天津大学 | Pressure type water electrolyser |
| CN101531765A (en) * | 2009-04-10 | 2009-09-16 | 天津大学 | Method for preparing sulfonated polymer films |
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