CN102329432A - Method for preparing sulfonic acid polymer proton exchange membrane - Google Patents
Method for preparing sulfonic acid polymer proton exchange membrane Download PDFInfo
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- CN102329432A CN102329432A CN201110210770A CN201110210770A CN102329432A CN 102329432 A CN102329432 A CN 102329432A CN 201110210770 A CN201110210770 A CN 201110210770A CN 201110210770 A CN201110210770 A CN 201110210770A CN 102329432 A CN102329432 A CN 102329432A
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for preparing a sulfonic acid polymer proton exchange membrane, which comprises the following steps of: adding sulfonic acid polymer into a polar aprotic solvent to obtain a sulfonic acid polymer solution; and heating the sulfonic acid polymer solution in steam environment to obtain the sulfonic acid polymer proton exchange membrane. A method of inducing phase transition through steam is adopted, and the sulfonic acid polymer solution is heated in the steam environment; and because the polar aprotic solvent in the sulfonic acid polymer solution has good intermiscibility with the steam, the steam is continuously diffused to the sulfonic acid polymer solution in the film forming process, the sulfonic acid polymer is subjected to phase separation and a polymer lean phase and a polymer rich phase are formed. Under the drive of concentration difference of water between two phases, the polar aprotic solvent in the polar aprotic solvent carries sulfonic acid groups to migrate to the surface of the polymer rich phase, and a proton transmission channel is formed, so that the proton transmissivity of the prepared sulfonic acid polymer proton exchange membrane is improved.
Description
Technical field
The present invention relates to the PEM technical field, more particularly, relate to a kind of preparation method of sulfonic acid-based polymer PEM.
Background technology
PEM is one of core component of Proton Exchange Membrane Fuel Cells and direct alcohol fuel battery; Its effect mainly shows the anode and the negative electrode of the following aspects (1) separate batteries, stops fuel that chemical reaction took place with direct mixing of air or oxygen; (2) proton conducting, the proton conductivity of PEM is high more, and its internal resistance is more little, thus the efficient of fuel cell is high more; (3) stop the conduction of electronics in film as electrical insulator, make electronics by anode through outside line road direction cathode flow, the generation foreign current.
Sulfonic acid proton exchange film be one type with the sulfonic acid group PEM of carrier in return, be the one type of very important proton exchange membrane material that is applied at present in the Proton Exchange Membrane Fuel Cells.In sulfonic acid proton exchange film, proton is assembled the ion cluster that forms through sulfonic acid group and is conducted, and therefore, the ion cluster that sulfonic acid group is assembled formation is many more, and the proton conductivity of sulfonic acid proton exchange film is strong more.Traditional sulfonic acid proton exchange film is prepared by solution film casting method, mainly may further comprise the steps: prepared polymer solution, then the polymers soln of preparation is dried in baking oven, and finally form proton transmission film.
At present; Sulfonic acid proton exchange film and preparation method thereof has obtained report widely; For example; Application number a kind of compound proton exchange membrane that has been 201010195365.6 Chinese patent bibliographical information, its preparation method is: the mixing solutions that with sulfonation degree is 50～70% sulfonated polyether-ether-ketone solution, polyaniline filtrating and heteropolyacid obtains compound proton exchange membrane through casting film-forming, drying.Because this method is directly carried out the processing of solvent flashing to mixing solutions in preparation sulfonic acid proton exchange film process; The control of arrangement that can not the p-sulfonic acid group; Thereby the sulfonic acid group of prepared sulfonic acid proton exchange film forms the invalid sulfonic acid group of much not participating in proton conduction; Can not be completed into ion cluster, so the utilization ratio of sulfonic acid group is not high, the proton conductivity of the sulfonic acid proton exchange film that causes preparing is lower.
Summary of the invention
In view of this, the technical problem that the present invention will solve is to provide a kind of preparation method of sulfonic acid-based polymer PEM, and this method prepares the sulfonic acid-based polymer PEM and has higher proton conductivity.
In order to solve the problems of the technologies described above, the present invention provides a kind of preparation method of sulfonic acid-based polymer PEM, may further comprise the steps:
Step a) adds sulfonic acid-based polymer in aprotic polar solvent, obtain sulfonic acid-based polymer solution;
Step b) heats said sulfonic acid-based polymer solution under the environment of water vapour, obtain the sulfonic acid-based polymer PEM.
Preferably, said aprotic polar solvent is N, dinethylformamide or DMAC N,N.
Preferably, said sulfonic acid-based polymer is that sulfonation degree is 10%～60% sulfonated polyether-ether-ketone.
Preferably, the concentration of said sulfonic acid-based polymer solution is 50～300mg/ml.
Preferably, the pressure of said water vapour is 2.33kPa～70kPa.
Preferably, said step b) is specially:
Step b1) in encloses container, adds entry, be heated to 40～90 ℃;
Step b2) said sulfonic acid-based polymer solution is warming up to 40～90 ℃ and insulation in said encloses container, obtains primary membrane;
Step b3) said primary membrane is warming up to 100～120 ℃ and insulation, obtains the sulfonic acid-based polymer PEM.
Preferably, Heating temperature said step b1) is 60～80 ℃.
Preferably, said step b2) be specially:
Step b21) substrate is placed in the encloses container;
Step b22) said sulfonic acid-based polymer solution is applied and said substrate surface, be warming up to 60～80 ℃ and be incubated 2～5 hours, obtain primary membrane.
Preferably, intensification temperature said step b3) is 110 ℃.
Preferably, soaking time said step b3) is 0.5～2 hour.
The present invention provides a kind of preparation method of sulfonic acid-based polymer PEM, may further comprise the steps: step a) adds sulfonic acid-based polymer in aprotic polar solvent, obtains sulfonic acid-based polymer solution; Step b) heats said sulfonic acid-based polymer solution under the environment of water vapour, obtain the sulfonic acid-based polymer PEM.Compared with prior art; The present invention adopts water vapour induction phase method of converting; Sulfonic acid-based polymer solution is heated under the environment of water vapour, because aprotic polar solvent in the sulfonic acid-based polymer solution and water vapour and good intermiscibility, water vapour constantly spreads in sulfonic acid-based polymer solution in film process; Sulfonic acid-based polymer is separated, and it is stingy rich mutually with polymkeric substance to form polymkeric substance.Under the motivating force of the concentration difference of water between two phases; Aprotic polar solvent band in the sulfonic acid-based polymer solution sulfonic acid group to the rich phase surface migration of polymkeric substance; Form the passage of proton transport, thereby improved the proton conductivity of the sulfonic acid-based polymer PEM of preparation.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art; To do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below; Obviously, the accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills; Under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the ESEM picture of the sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) of the embodiment of the invention 1 preparation;
Fig. 2 is the x-ray photoelectron spectrum curve of the sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) of the embodiment of the invention 1 preparation;
Fig. 3 is the ESEM picture of the sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) of the embodiment of the invention 2 preparations;
Fig. 4 is the x-ray photoelectron spectrum curve of the sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) of the embodiment of the invention 2 preparations;
Fig. 5 is the ESEM picture of the sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) of the embodiment of the invention 3 preparations;
Fig. 6 is the x-ray photoelectron spectrum curve of the sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) of the embodiment of the invention 3 preparations;
Fig. 7 is the ESEM picture of the sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) of comparative example preparation of the present invention;
Fig. 8 is the x-ray photoelectron spectrum curve of the sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) of comparative example preparation of the present invention.
Embodiment
Carry out clear, intactly description in the face of the technical scheme in the embodiment of the invention down, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
The invention discloses a kind of preparation method of sulfonic acid-based polymer PEM, may further comprise the steps:
Step a) adds sulfonic acid-based polymer in aprotic polar solvent, obtain sulfonic acid-based polymer solution;
Step b) heats said sulfonic acid-based polymer solution under the environment of water vapour, obtain the sulfonic acid-based polymer PEM.
In step a), said aprotic polar solvent is preferably N, dinethylformamide or DMAC N,N.It is 10%～60% sulfonic acid-based polymer that said sulfonic acid-based polymer is preferably sulfonation degree, and more preferably sulfonation degree is 10%～60% sulfonated polyether-ether-ketone, most preferably is sulfonation degree and is 30%～50% sulfonated polyether-ether-ketone.The concentration of said sulfonic acid-based polymer solution is preferably 50～300mg/ml, and more preferably 100～200mg/ml most preferably is 100mg/ml.The pressure of said water vapour is preferably 2.33kPa～70kPa, and more preferably 10kPa～50kPa most preferably is 20kPa～30kPa.Saidly in aprotic polar solvent, add preferred the stirring 15～30 hours behind the sulfonic acid-based polymer, leave standstill de-bubble in 15～30 hours then, thereby obtain uniform sulfonic acid-based polymer solution.
The present invention adopts water vapour induction phase method of converting; Sulfonic acid-based polymer solution is heated under the environment of water vapour; Because aprotic polar solvent in the sulfonic acid-based polymer solution and water vapour and good intermiscibility; Water vapour constantly spreads in sulfonic acid-based polymer solution in film process, and sulfonic acid-based polymer is separated, and it is stingy rich mutually with polymkeric substance to form polymkeric substance.Under the motivating force of the concentration difference of water between two phases; Aprotic polar solvent band in the sulfonic acid-based polymer solution sulfonic acid group to the rich phase surface migration of polymkeric substance; Form the passage of proton transport, improved the proton conductivity of the sulfonic acid-based polymer PEM of preparation.
Among the present invention, said step b) is preferably: step b1) in encloses container, add entry, be heated to 40～90 ℃; Step b2) said sulfonic acid-based polymer solution is warming up to 40～90 ℃ and insulation in said encloses container, obtains primary membrane; Step b3) said primary membrane is warming up to 100～120 ℃ and insulation, obtains the sulfonic acid-based polymer PEM.The present invention makes water realize evaporation at a certain temperature, thereby obtains water vapour through in encloses container, adding entry and heating.Wherein, said step b1) Heating temperature is preferably 60～80 ℃, more preferably 70～80 ℃, is preferably 1～3 hour heat-up time, more preferably 1 hour.Said step b1) is specially, in encloses container, adds beaker, in said beaker, add zero(ppm) water, then said encloses container is heated to 40～90 ℃.
At step b2) in, its intensification temperature is preferably 60～80 ℃, more preferably 70～80 ℃.Said step b2) is specially: step b21) substrate is placed in the encloses container; Step b22) said sulfonic acid-based polymer solution is applied and said substrate surface, be warming up to 60～80 ℃ and be incubated 2～5 hours, obtain primary membrane.The present invention does not have special restriction to said substrate, can be sheet glass etc.In this step; Carried out exchange of substance between polymers soln and the water vapor atmosphere; The aprotic polar solvent of polymers soln diffuses in the water vapor atmosphere, and water vapour molecule gets in the polymers soln in the water vapor atmosphere, thereby carries out the sulfonic arrangement of inducing.
In addition, at step b2) in, along with the carrying out of heating up and being incubated, the pressure of water vapour increases gradually.Along with the vapour content in the environment increases; The concentration difference of solvent becomes increasing between polymer nanocomposite intra-zone and the surface; This concentration difference is an aprotic polar solvent provides bigger power to water mobile; Therefore, the effect owing to concentration difference of sulfonic acid group is transferred to the passage that particle surface forms proton transport, thereby has further improved proton conductivity.
After obtaining primary membrane, with primary membrane be warming up to 100～120 ℃ and the insulation, said step b3) the intensification temperature be preferably 110 ℃, soaking time is preferably 0.5～2 hour, more preferably 1～2 hour.Through of the further heating of this step, thoroughly removed the aprotic polar solvent in the primary membrane to primary membrane.
In order to further specify technical scheme of the present invention; Below in conjunction with embodiment the preferred embodiment of the invention is described; Describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
Embodiment 1
(1) preparation preparation liquid: take by weighing sulfonation degree and be 40% sulfonated polyether-ether-ketone 400mg, join in the 10ml beaker, add 4ml N, dinethylformamide, at stirring at room 24h, static afterwards 24h de-bubble;
(2) shop film: get one of the watertight chest of 10cm*20cm*10cm, the water bag of the about 5cm of bottom shop thickness in case is in order to the adjusting level; The other 50ml beaker of placing of water bag injects 40ml zero(ppm) water in the beaker, it is 40 ℃ that watertight chest is put into the baking oven preheating; Behind the preheating 1h, take out watertight chest, the sheet glass of 5cm*5cm is placed on the water bag; Be adjusted to horizontality; The preparation liquid that stirs is laid on the film uniformly, and sealing cover is buckled well and is placed on baking oven internal heating to 40 ℃ insulation 3h, 20 ℃ of baking oven internal cooling to room temperatures;
The sheet glass that (3) will be covered with the sulfonated polyether-ether-ketone film was in 110 ℃ of heating 1 hour, and taking-up places zero(ppm) water subsequent use.
The sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) proton conductivity of present embodiment preparation is 0.009Scm
-1As shown in Figure 1, be the ESEM picture of the sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) of present embodiment preparation; As shown in Figure 2, be the x-ray photoelectron spectrum curve of the sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) of present embodiment preparation.
Embodiment 2
(1) preparation preparation liquid: take by weighing sulfonation degree and be 40% sulfonated polyether-ether-ketone 400mg and join in the 10ml beaker, add 4ml N then, dinethylformamide, at stirring at room 24h, static afterwards 24h de-bubble;
(2) shop film: get one of 10cm*20cm*10cm watertight chest, the water bag of the about 5cm of bottom shop thickness in case is in order to the adjusting level; The other 50ml beaker of placing of water bag injects 40ml zero(ppm) water in the beaker, it is 60 ℃ that watertight chest is put into the baking oven preheating; Behind the preheating 1h, take out watertight chest, the sheet glass of 5cm*5cm is placed on the water bag; Be adjusted to horizontality; The preparation liquid that stirs is laid on the film uniformly, and sealing cover is buckled well and is placed on baking oven internal heating to 60 ℃ insulation 3h, 20 ℃ of baking oven internal cooling to room temperatures;
The sheet glass that (3) will be covered with the sulfonated polyether-ether-ketone film was in 110 ℃ of heating 1 hour, and taking-up places zero(ppm) water subsequent use.
The sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) proton conductivity of present embodiment preparation is 0.015Scm
-1, as shown in Figure 3, be the ESEM picture of the sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) of present embodiment preparation; As shown in Figure 4, be the x-ray photoelectron spectrum curve of the sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) of present embodiment preparation.
Embodiment 3
(1) preparation preparation liquid: take by weighing sulfonation degree and be 40% sulfonated polyether-ether-ketone 400mg, join in the 10ml beaker, add 4ml N, dinethylformamide, at stirring at room 24h, static afterwards 24h de-bubble;
(2) shop film: get one of 10cm*20cm*10cm watertight chest, the water bag of the about 5cm of bottom shop thickness in case is in order to the adjusting level; The other 50ml beaker of placing of water bag injects 40ml zero(ppm) water in the beaker, it is 80 ℃ that watertight chest is put into the baking oven preheating; Behind the preheating 1h, take out watertight chest, the sheet glass of 5cm*5cm is placed on the water bag; Be adjusted to horizontality; The preparation liquid that stirs is laid on the film uniformly, and sealing cover is buckled well and is placed on baking oven internal heating to 80 ℃ insulation 3h, 20 ℃ of baking oven internal cooling to room temperatures;
The sheet glass that (3) will be covered with the sulfonated polyether-ether-ketone film was in 110 ℃ of heating 1 hour, and taking-up places zero(ppm) water subsequent use.
The sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) proton conductivity of present embodiment preparation is 0.02Scm
-1As shown in Figure 5, be the ESEM picture of the sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) of present embodiment preparation; As shown in Figure 6, be the x-ray photoelectron spectrum curve of the sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) of present embodiment preparation.
Comparative example
(1) preparation preparation liquid: take by weighing sulfonation degree and be 40% sulfonated polyether-ether-ketone 400mg, join in the 10ml beaker, add 4ml N, dinethylformamide, at stirring at room 24h, static afterwards 24h de-bubble;
(2) sheet glass with 5cm*5cm places on the water bag, is adjusted to horizontality, the preparation liquid that stirs is laid on the film uniformly static 3 days of room temperature;
(3) film is taken off place zero(ppm) water, obtain sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM).
The sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) proton conductivity of this comparative example preparation is 0.007Scm
-1As shown in Figure 7, be the ESEM picture of the sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) of this comparative example preparation; As shown in Figure 8, be the x-ray photoelectron spectrum curve of the sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) of this comparative example preparation.
Can find out that through the foregoing description and comparative example the proton conductivity through the prepared PEM of traditional film-forming method in the comparative example is 0.007S/cm
-1, and the present invention can reach 0.02Scm through the high proton conductivity that changes the prepared sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) of system embrane method mutually
-1Thereby the arrangement of sulfonic acid group has received better controlled among explanation the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. the preparation method of a sulfonic acid-based polymer PEM may further comprise the steps:
Step a) adds sulfonic acid-based polymer in aprotic polar solvent, obtain sulfonic acid-based polymer solution;
Step b) heats said sulfonic acid-based polymer solution under the environment of water vapour, obtain the sulfonic acid-based polymer PEM.
2. preparation method according to claim 1 is characterized in that, said aprotic polar solvent is N, dinethylformamide or DMAC N,N.
3. preparation method according to claim 1 is characterized in that, said sulfonic acid-based polymer is that sulfonation degree is 10%～60% sulfonated polyether-ether-ketone.
4. preparation method according to claim 1 is characterized in that, the concentration of said sulfonic acid-based polymer solution is 50～300mg/ml.
5. preparation method according to claim 1 is characterized in that, the pressure of said water vapour is 2.33kPa～70kPa.
6. preparation method according to claim 1 is characterized in that, said step b) is specially:
Step b1) in encloses container, adds entry, be heated to 40～90 ℃;
Step b2) said sulfonic acid-based polymer solution is warming up to 40～90 ℃ and insulation in said encloses container, obtains primary membrane;
Step b3) said primary membrane is warming up to 100～120 ℃ and insulation, obtains the sulfonic acid-based polymer PEM.
7. preparation method according to claim 6 is characterized in that, said step b1) Heating temperature be 60～80 ℃.
8. preparation method according to claim 6 is characterized in that, said step b2) be specially:
Step b21) substrate is placed in the encloses container;
Step b22) said sulfonic acid-based polymer solution is applied and said substrate surface, be warming up to 60～80 ℃ and be incubated 2～5 hours, obtain primary membrane.
9. preparation method according to claim 6 is characterized in that, said step b3) the intensification temperature be 110 ℃.
10. preparation method according to claim 6 is characterized in that, said step b3) soaking time be 0.5～2 hour.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102623733A (en) * | 2012-04-11 | 2012-08-01 | 北京化工大学 | Preparation method of proton exchange membrane with nanometer pore structure |
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| CN101864163A (en) * | 2010-06-08 | 2010-10-20 | 南通大学 | Preparation method of composite proton exchange membrane |
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| CN101771159A (en) * | 2010-01-26 | 2010-07-07 | 新奥科技发展有限公司 | Proton exchange membrane and preparation method thereof |
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Application publication date: 20120125 |