CN112510236A - Proton exchange membrane and preparation method and application thereof - Google Patents
Proton exchange membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a proton exchange membrane and a preparation method and application thereof. The proton exchange membrane provided by the invention has the characteristics of good proton conductivity, stability of the proton conductivity, mechanical performance and the like, and can improve the quality of the fuel cell such as energy conversion rate, service life and the like; in addition, the preparation method for in-situ synthesis of the proton exchange membrane has the advantages of simple preparation process, low cost, environmental protection and the like, and has important practical significance in industry.
Description
Technical Field
The invention relates to a proton exchange membrane and a preparation method and application thereof, belonging to the field of fuel cells.
Background
Proton Exchange Membranes (PEMs) are important as core components of Proton Exchange Membrane Fuel Cells (PEMFCs) in the operation of the fuel cells, and ideal PEM is expected to have high proton conductivity and excellent mechanical properties.
Covalent Organic Frameworks (COFs) are a class of crystalline porous materials that are predominantly produced by covalent bonding of lighter elements (e.g., bc no) in a periodic fashion, and have received much attention due to their chemical tunability, high porosity, and ordered structural integrity. Film-like materials based on COF have been studied and reported, for example, Sasmal et al (angelw.chem.int.ed.2018, 57,10894.) disclose a COF-based film material, which mainly loads small-molecule proton carriers in situ in COF for proton conduction; in addition, a film material with a polymer introduced into the COF, for example, Xie et al (angelw. chem. int.ed.2019,58,15742) introduces polyethylene glycol (PEG) into the COF matrix, so that the proton conductivity is improved to some extent by the synergistic effect of PEG and water.
Although COF can be used as a substrate or a raw material of a membrane material such as a proton exchange membrane, on one hand, due to high crystallinity of COF, the conventional membrane material has poor mechanical properties, which are mainly manifested in the aspects of brittleness, easy cracking and the like, and on the other hand, to meet performance requirements of the proton exchange membrane such as electrical conductivity and the like, components such as proton carriers (such as p-toluenesulfonic acid and the like) are usually introduced into COF, but due to water solubility and the like, the proton carriers distributed in pore channels of COF are easy to run off, and characteristics of the proton exchange membrane such as proton transport efficiency and the like are affected.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a proton exchange membrane having both good proton conductivity and proton conductivity stability and good mechanical properties.
The invention also provides a preparation method of the proton exchange membrane, which can be used for preparing the proton exchange membrane and has the advantages of simple preparation process, low cost, environmental protection and the like.
The invention also provides an application of the proton exchange membrane in a fuel cell, and the proton exchange membrane is applied to the fuel cell, so that the energy conversion rate, the service life and other qualities of the fuel cell can be improved.
In one aspect of the invention, a proton exchange membrane is provided, comprising a covalent organic framework material and an ionic polymer complexed with the covalent organic framework material.
The proton exchange membrane provided by the invention has good proton conductivity, good proton conductivity stability and mechanical properties, and the inventor considers through research and analysis that ionic polymers are introduced into a COF matrix, rather than acid-base ion pairs constructed by introducing cationic groups and anionic groups into the COF matrix, the ionic polymers are filled in a pore channel of the COF as proton carriers, and the ionic polymers are not easy to lose through the ionic interaction between the COF and ionic polymer objects, and the proton conductivity, stability and other properties of the proton exchange membrane can be remarkably improved through the synergistic cooperation of the ionic polymers and the COF.
According to the research of the invention, the covalent organic framework material generally comprises a ketone enamine material obtained by a Schiff base reaction of a diamino monomer and an aldehyde group monomer, and is beneficial to further improving the properties of proton conductivity, mechanical property and the like of the proton exchange membrane.
In particular, the number of moles of the diamino monomer is generally greater than the number of moles of the aldehyde monomer, and in a preferred embodiment, the molar ratio of the diamino monomer to the aldehyde monomer may be 1.2 to 1.5: 1.
Specifically, the diamine monomer may include p-phenylenediamine (hereinafter, referred to as Pa-1) and 2, 5-diaminobenzenesulfonic acid (hereinafter, referred to as Pa-SO)3H) 1, 4-disulfonic acid-2, 5-diaminobenzene (hereinafter referred to as Pa- (SO)3H)2) 4,4' -diaminobiphenyl (hereinafter referred to as Bd) and benzidine disulfonic acid (hereinafter referred to as Bd- (SO)3H)2) At least one of 1, 4-diaminopyridine (hereinafter, Py) and 4,4 '-diamino-2, 2' -bipyridine (hereinafter, BPy); further, the aldehyde-based monomer includes 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid (hereinafter, Tp). By synthesis from such monomersThe COF is beneficial to further improving the properties of the proton exchange membrane, such as proton conductivity, mechanical properties and the like, and is supposed to be because the COF synthesized by the diamino monomer with the sulfonic acid or pyridine groups and the aldehyde group monomer is beneficial to introducing acidic or basic ionic groups into the COF, and further enhances the interaction between the COF and the ionic polymer, thereby improving the performance of the proton exchange membrane.
Further, the ionic polymer with sulfonic acid group or imine group or quaternary ammonium ionic polymer is used to facilitate the performance of proton exchange membrane, and in a preferred embodiment of the present invention, the ionic polymer may include at least one of poly (4-styrenesulfonic acid) (PSS), Polyethyleneimine (PEI), and polydiallyldimethylammonium chloride (PDDA).
Further, the weight average molecular weight of the ionic polymer may be generally 70000 to 500000.
Through further research, the ionic polymer is introduced into the COF through an in-situ loading process, which is more beneficial to the properties of proton conductivity, mechanical properties and the like of the proton exchange membrane, and specifically, in a preferred embodiment of the invention, the proton exchange membrane can be prepared according to a preparation process comprising the following steps: coating slurry containing covalent organic framework material synthetic monomers and ionic polymers to form a wet membrane, and carrying out Schiff base reaction to obtain the proton exchange membrane; wherein the synthetic monomer comprises a diamino monomer and an aldehyde monomer.
In another aspect of the present invention, a method for preparing a proton exchange membrane is provided, which comprises: coating slurry containing covalent organic framework material synthetic monomers and ionic polymers to form a wet membrane, and carrying out Schiff base reaction to obtain the proton exchange membrane; wherein the synthetic monomer comprises a diamino monomer and an aldehyde monomer.
In specific implementation, the amino monomers and the aldehyde monomers and other synthetic monomers are firstly ground and mixed, the ionic polymer and water are added into the obtained mixture powder, and then the mixture powder is ground and mixed to form the slurry. Wherein, the addition of water can meet the condition that the components are mixed to form slurry, and during the specific operation, the mixture powder and the aqueous solution of the ionic polymer can be mixed to form slurry, and the concentration of the slurry can be regulated by additionally adding proper amount of water so as to be easier to coat and form a film.
Generally, the slurry is subjected to a defoaming treatment, for example, the slurry can be placed in a vacuum box to be vacuumized to remove air bubbles possibly existing in the slurry (i.e., defoaming treatment), and then the slurry is coated to form a wet film.
Specifically, the mass ratio of the ionic polymer to the synthetic monomer of the covalent organic framework material may be (1-15): 100.
in order to facilitate the reaction, the slurry can also comprise a catalyst, and the molar ratio of the catalyst to the synthetic monomer can be (2-5): 1.
further, the above catalyst may include p-toluenesulfonic acid (PTSA). According to the research of the application, the p-toluenesulfonic acid is introduced in the preparation process, so that the proton conductivity and other properties of the proton exchange membrane can be further improved, and the speculated reason is that the p-toluenesulfonic acid can not only catalyze the reaction, but also can be sealed in the pore channel of the formed COF to provide a new proton transmission site, so that the proton transmission capability of the proton exchange membrane is improved. For the specific operation, p-toluenesulfonic acid monohydrate (PTSA. H) is usually used2O) is used as a catalyst.
In a preferred embodiment of the present invention, generally, the amino monomer and the p-toluenesulfonic acid are mixed and then ground into powder, then the aldehyde monomer is added into the powder, the mixture is continuously ground and uniformly mixed, and then the ionic polymer and water are added into the obtained mixture powder to form the slurry, which is more beneficial to subsequent treatment and preparation of the proton exchange membrane with excellent properties such as proton conductivity.
The present invention can apply the above-mentioned slurry to a wet film by a method conventional in the art, and for example, the above-mentioned slurry (paste) can be applied to a substrate such as a glass plate using a coater to form a wet film, or the above-mentioned slurry can be placed in a mold to form a wet film, etc., which is not particularly limited.
In the above preparation process, the schiff base reaction may be generally performed by a stepwise heating reaction, and in a preferred embodiment of the present invention, the schiff base reaction process includes: under the condition of normal pressure (namely the pressure is 1 atm), the wet membrane is reacted for 12 to 24 hours at the temperature of between 50 and 60 ℃, then the temperature is increased to between 80 and 90 ℃ for reaction for 12 to 24 hours, and then the temperature is increased to between 105 and 120 ℃ for reaction for 12 to 24 hours, so as to obtain the proton exchange membrane.
After the schiff base reaction is finished, washing the obtained membrane product by using solvents such as Dichloromethane (DCM) and acetone to remove impurities such as unreacted monomers and oligomers which may exist, removing the membrane product from a mold or a substrate, and drying the membrane product to obtain the proton exchange membrane, wherein the drying temperature may be 40 ± 5 ℃.
In still another aspect of the present invention, there is also provided a use of the proton exchange membrane in a fuel cell.
The implementation of the invention has at least the following beneficial effects:
the proton exchange membrane provided by the invention is a novel COF substrate proton exchange membrane, has good proton conductivity and proton conductivity stability, is high in mechanical strength, not easy to break and long in service life, and has important practical significance in industry.
The preparation method of the proton exchange membrane provided by the invention has the advantages that the proton exchange membrane is synthesized in situ, so that the proton exchange membrane has the characteristics of good proton conductivity, stability of the proton conductivity, mechanical property and the like, the preparation process is simple, the condition is mild, a large amount of organic solvents are not needed, the cost is low, the environment is protected, and the method is beneficial to actual industrial production and application.
The proton exchange membrane fuel cell provided by the invention has the advantages of high energy conversion rate, long service life and the like by adopting the proton exchange membrane.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The proton exchange membrane provided in this example was prepared as follows:
(1) 56.5mg (0.3mmol) of Pa-SO3H and 285mg (1.5mmol) PTSA. H2Adding O into a mortar, grinding and mixing uniformly, then adding 42mg (0.2mmol) of Tp, and further grinding uniformly to obtain mixture powder;
(2) adding 98.5mg of PDDA aqueous solution with the mass concentration of 1% and 202 mu l of deionized water into the mixture powder, and grinding and uniformly mixing to form mixed slurry; placing the mixed slurry in a vacuum box, vacuumizing at room temperature until the pressure is 0.5bar, and keeping for 5min to defoam the mixed slurry; wherein the weight average molecular weight of the PDDA is 450000;
(3) uniformly coating the defoamed mixed slurry on a glass plate by using a film coater with the thickness of 250 mu m to form a wet film with the thickness of 250 mu m;
(4) placing the glass plate in an oven, firstly preserving heat at 60 ℃ for 12h, then heating to 90 ℃ and preserving heat for 12h, and then heating to 120 ℃ and preserving heat for 12 h; and soaking the obtained film-shaped product and a glass plate in DCM for 30min, then taking off the film-shaped product from the glass plate, washing the film-shaped product by using DCM and acetone in sequence, and drying the film-shaped product for 8h at 40 ℃ to obtain the proton exchange membrane.
Example 2
(1) 80.5mg (0.3mmol) of Pa- (SO)3H)2And 285.3mg (1.5mmol) of PTSA. H2Adding O into a mortar, grinding and uniformly mixing, then adding 42mg (0.2mmol) of Tp, and further grinding and uniformly mixing to obtain mixture powder;
(2) adding 184mg of PDDA aqueous solution with the mass concentration of 10% and 216 mu l of deionized water into the mixture powder, and grinding and uniformly mixing to form mixed slurry; placing the mixed slurry in a vacuum box, vacuumizing at room temperature until the pressure is 0.5bar, and keeping for 5min to defoam the mixed slurry; wherein the weight average molecular weight of the PDDA is 500000;
(3) uniformly coating the defoamed mixed slurry on a glass plate by using a film coater with the thickness of 250 mu m to form a wet film with the thickness of 250 mu m;
(4) placing the glass plate in an oven, firstly preserving heat at 60 ℃ for 12h, then heating to 80 ℃ and preserving heat for 12h, and then heating to 120 ℃ and preserving heat for 12 h; and soaking the obtained film-shaped product and a glass plate in DCM for 30min, then taking off the film-shaped product from the glass plate, washing the film-shaped product by using DCM and acetone in sequence, and drying the film-shaped product for 8h at 40 ℃ to obtain the proton exchange membrane.
Example 3
(1) 103.3mg (0.3mmol) of Bd- (SO)3H)2And 285.3mg (1.5mmol) of PTSA. H2Adding O into a mortar, grinding and uniformly mixing, then adding 42mg (0.2mmol) of Tp, and further grinding and uniformly mixing to obtain mixture powder;
(2) adding 72.5mg of PEI aqueous solution with the mass concentration of 10% and 427 mu l of deionized water into the mixture powder, and grinding and uniformly mixing to form mixed slurry; placing the mixed slurry in a vacuum box, vacuumizing at room temperature until the pressure is 0.5bar, and keeping for 5min to defoam the mixed slurry; wherein the weight average molecular weight of PEI is 180000;
(3) uniformly coating the defoamed mixed slurry on a glass plate by using a film coater with the thickness of 250 mu m to form a wet film with the thickness of 250 mu m;
(4) placing the glass plate in an oven, firstly preserving heat at 60 ℃ for 12h, then heating to 90 ℃ and preserving heat for 12h, and then heating to 105 ℃ and preserving heat for 12 h; and soaking the obtained film-shaped product and a glass plate in DCM for 30min, then taking off the film-shaped product from the glass plate, washing the film-shaped product by using DCM and acetone in sequence, and drying the film-shaped product for 8h at 40 ℃ to obtain the proton exchange membrane.
Example 4
(1) 32.7mg (0.3mmol) Py and 476mg (2.5mmol) PTSA. H2Adding O into a mortar, grinding and mixing uniformly, then adding 42mg (0.2mmol) of Tp, and further grinding uniformly to obtain mixture powder;
(2) adding 104.6mg of PSS aqueous solution with the mass concentration of 5% and 395 ul of deionized water into the mixture powder, grinding and uniformly mixing to form mixed slurry; placing the mixed slurry in a vacuum box, vacuumizing at room temperature until the pressure is 0.5bar, and keeping for 5min to defoam the mixed slurry; wherein the PSS has a weight average molecular weight of 70000;
(3) uniformly coating the defoamed mixed slurry on a glass plate by using a film coater with the thickness of 250 mu m to form a wet film with the thickness of 250 mu m;
(4) placing the glass plate in an oven, preserving heat for 12h at 50 ℃, then heating to 90 ℃, preserving heat for 12h, and then heating to 120 ℃, preserving heat for 12 h; and soaking the obtained film-shaped product and a glass plate in DCM for 30min, then taking off the film-shaped product from the glass plate, washing the film-shaped product by using DCM and acetone in sequence, and drying the film-shaped product for 8h at 40 ℃ to obtain the proton exchange membrane.
Example 5
(1) 55.9mg (0.3mmol) of BPy and 380mg (2mmol) of PTSA. H2Adding O into a mortar, grinding and mixing uniformly, then adding 42mg (0.2mmol) of Tp, and further grinding uniformly to obtain mixture powder;
(2) adding 98mg of PSS aqueous solution with the mass concentration of 10% and 402 mul of deionized water into the mixture powder, and grinding and uniformly mixing to form mixed slurry; placing the mixed slurry in a vacuum box, vacuumizing at room temperature until the pressure is 0.5bar, and keeping for 5min to defoam the mixed slurry; wherein, the PSS has the weight-average molecular weight of 70000;
(3) uniformly coating the defoamed mixed slurry on a glass plate by using a film coater with the thickness of 250 mu m to form a wet film with the thickness of 250 mu m;
(4) placing the glass plate in an oven, firstly preserving heat at 60 ℃ for 12h, then heating to 85 ℃ and preserving heat for 12h, and then heating to 110 ℃ and preserving heat for 12 h; and soaking the obtained film-shaped product and a glass plate in DCM for 30min, then taking off the film-shaped product from the glass plate, washing the film-shaped product by using DCM and acetone in sequence, and drying the film-shaped product for 8h at 40 ℃ to obtain the proton exchange membrane.
Example 6
(1) 32.4mg (0.3mmol) of Pa-1 were mixed with190mg(1mmol)PTSA·H2Adding O into a mortar, grinding and mixing uniformly, then adding 42mg (0.2mmol) of Tp, and further grinding uniformly to obtain mixture powder;
(2) adding a PSS aqueous solution with the mass concentration of 37mg being 10%, a PDDA aqueous solution with the mass concentration of 37mg being 10% and 50 mu l of deionized water into the mixture powder, and grinding and uniformly mixing to form mixed slurry; placing the mixed slurry in a vacuum box, vacuumizing at room temperature until the pressure is 0.5bar, and keeping for 5min to defoam the mixed slurry; wherein the PSS has the weight-average molecular weight of 70000, and the PDDA has the weight-average molecular weight of 100000;
(3) uniformly coating the defoamed mixed slurry on a glass plate by using a film coater with the thickness of 250 mu m to form a wet film with the thickness of 250 mu m;
(4) placing the glass plate in an oven, firstly preserving heat at 55 ℃ for 12h, then heating to 90 ℃ and preserving heat for 12h, and then heating to 115 ℃ and preserving heat for 12 h; and soaking the obtained film-shaped product and a glass plate in DCM for 30min, then taking off the film-shaped product from the glass plate, washing the film-shaped product by using DCM and acetone in sequence, and drying the film-shaped product for 8h at 40 ℃ to obtain the proton exchange membrane.
Example 7
(1) 55.2mg (0.3mmol) of Bd and 190mg (1mmol) of PTSA. H2Adding O into a mortar, grinding and mixing uniformly, then adding 42mg (0.2mmol) of Tp, and further grinding uniformly to obtain mixture powder;
(2) adding 73mg of PSS aqueous solution with the mass concentration of 10%, 73mg of PDDA aqueous solution with the mass concentration of 10% and 20 mu l of deionized water into the mixture powder, and grinding and uniformly mixing to form mixed slurry; placing the mixed slurry in a vacuum box, vacuumizing at room temperature until the pressure is 0.5bar, and keeping for 5min to defoam the mixed slurry; wherein the PSS has the weight-average molecular weight of 70000, and the PDDA has the weight-average molecular weight of 100000;
(3) uniformly coating the defoamed mixed slurry on a glass plate by using a film coater with the thickness of 250 mu m to form a wet film with the thickness of 250 mu m;
(4) placing the glass plate in an oven, firstly preserving heat at 60 ℃ for 12h, then heating to 90 ℃ and preserving heat for 12h, and then heating to 115 ℃ and preserving heat for 12 h; and soaking the obtained film-shaped product and a glass plate in DCM for 30min, then taking off the film-shaped product from the glass plate, washing the film-shaped product by using DCM and acetone in sequence, and drying the film-shaped product for 8h at 40 ℃ to obtain the proton exchange membrane.
Comparative example 1
(1) 56.5mg (0.3mmol) of Pa-SO3H and 285mg (1.5mmol) PTSA. H2Adding O into a mortar, grinding and mixing uniformly, then adding 42mg (0.2mmol) of Tp, and further grinding uniformly to obtain mixture powder;
(2) adding 500 mu l of deionized water into the mixture powder, grinding and uniformly mixing to form mixed slurry; placing the mixed slurry in a vacuum box, vacuumizing at room temperature until the pressure is 0.5bar, and keeping for 5min to defoam the mixed slurry;
(3) uniformly coating the defoamed mixed slurry on a glass plate by using a film coater with the thickness of 250 mu m to form a wet film with the thickness of 250 mu m;
(4) placing the glass plate in an oven, firstly preserving heat at 60 ℃ for 12h, then heating to 90 ℃ and preserving heat for 12h, and then heating to 120 ℃ and preserving heat for 12 h; and soaking the obtained film-shaped product and a glass plate in DCM for 30min, then taking off the film-shaped product from the glass plate, washing the film-shaped product by using DCM and acetone in sequence, and drying the film-shaped product for 8h at 40 ℃ to obtain the proton exchange membrane.
Comparative example 2
(1) 32.4mg (0.3mmol) of Pa-1 and 190mg (1.0mmol) of PTSA. H2Adding O into a mortar, grinding and mixing uniformly, then adding 42mg (0.2mmol) of Tp, and further grinding uniformly to obtain mixture powder;
(2) adding 500 mu l of deionized water into the mixture powder, grinding and uniformly mixing to form mixed slurry; placing the mixed slurry in a vacuum box, vacuumizing at room temperature until the pressure is 0.5bar, and keeping for 5min to defoam the mixed slurry;
(3) uniformly coating the defoamed mixed slurry on a glass plate by using a film coater with the thickness of 250 mu m to form a wet film with the thickness of 250 mu m;
(4) placing the glass plate in an oven, firstly preserving heat at 60 ℃ for 12h, then heating to 90 ℃ and preserving heat for 12h, and then heating to 115 ℃ and preserving heat for 12 h; and soaking the obtained film-shaped product and a glass plate in DCM for 30min, then taking off the film-shaped product from the glass plate, washing the film-shaped product by using DCM and acetone in sequence, and drying the film-shaped product for 8h at 40 ℃ to obtain the proton exchange membrane.
And (3) performance testing:
the proton conductivity of the proton exchange membranes of the examples and comparative examples was measured as follows: placing a proton exchange membrane on two parallel platinum sheets, and testing the alternating current impedance of the proton exchange membrane in pure water at 60 ℃ by using an electrochemical workstation (CHI660E), wherein the frequency range is 10Hz to 10MHz, and the testing environment is 100% RH; and proton conductivity was calculated by the following formula: where σ (S/cm) represents proton conductivity, L (cm) represents a distance between the two electrodes, R (Ω) represents an impedance value of the proton exchange membrane, and a (cm) represents2) The cross-sectional area of the proton exchange membrane sample is shown.
According to the test process, after the proton exchange membrane is subjected to primary test, the proton exchange membrane is soaked in deionized water at normal temperature for 7 days, then the proton conductivity of the proton exchange membrane is tested again according to the test process, and the loss condition of the proton carrier is verified.
Initial proton conductivity test and proton conductivity after 7 days of soaking of the proton exchange membranes of each example and comparative example were measured as shown in table 1.
In addition, the proton exchange membranes of the respective examples and comparative examples were bent as much as possible, and whether they were broken or not was observed to verify the mechanical properties, and the results are shown in table 1.
TABLE 1 measurement results of Properties of the proton exchange membranes of examples 1 to 7 and comparative examples 1 to 2
As can be seen from table 1, the proton exchange membranes of examples 1-7 have very excellent proton conductivity and a very small decrease in proton conductivity after being soaked for 7 days, compared to comparative examples 1 and 2, which indicates that the proton carriers in the proton exchange membranes of examples 1-7 are not easy to run off and have very strong stability of proton conductivity, and at the same time, the proton exchange membranes of examples 1-7 do not break after being bent and also exhibit good mechanical properties.
While the invention has been described with reference to specific embodiments, those skilled in the art will appreciate that various changes can be made without departing from the true spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation, material, composition of matter, and method to the essential scope and spirit of the present invention. All such modifications are intended to be included within the scope of the claims of this invention.
Claims (10)
1. A proton exchange membrane comprising a covalent organic framework material and an ionic polymer complexed with the covalent organic framework material.
2. The proton exchange membrane according to claim 1, wherein the covalent organic framework material comprises a ketoenamine material obtained by a schiff base reaction between a diamino monomer and an aldehyde monomer.
3. The proton exchange membrane according to claim 2, wherein the diamino monomer comprises at least one of p-phenylenediamine, 2, 5-diaminobenzene sulfonic acid, 1, 4-disulfonic acid-2, 5-diaminobenzene, 4 '-diaminobiphenyl, benzidine disulfonic acid, 1, 4-diaminopyridine, 4' -diamino-2, 2 '-bipyridine, p-phenylenediamine, 4' -diaminobiphenyl; and/or the aldehyde monomer comprises 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic aldehyde.
4. The proton exchange membrane according to claim 1 or 2, wherein the ionic polymer comprises at least one of poly (4-styrenesulfonic acid), polyethyleneimine, polydiallyldimethylammonium chloride; and/or the weight-average molecular weight of the ionic polymer is 70000-500000.
5. The proton exchange membrane according to claim 1 or 2, wherein the proton exchange membrane is prepared by a preparation process comprising the following steps: coating slurry containing covalent organic framework material synthetic monomers and ionic polymers to form a wet membrane, and carrying out Schiff base reaction to obtain the proton exchange membrane; wherein the synthetic monomer comprises a diamino monomer and an aldehyde monomer.
6. The process for the preparation of a proton exchange membrane according to any one of claims 1 to 5, comprising: coating slurry containing covalent organic framework material synthetic monomers and ionic polymers to form a wet membrane, and carrying out Schiff base reaction to obtain the proton exchange membrane; wherein the synthetic monomer comprises a diamino monomer and an aldehyde monomer.
7. The preparation method according to claim 6, wherein the mass ratio of the ionic polymer to the synthetic monomer of the common organic framework material is (1-15): 100.
8. the preparation method according to claim 6 or 7, characterized in that the slurry further comprises a catalyst, and the molar ratio of the catalyst to the synthetic monomer is (2-5): 1;
preferably, the catalyst comprises p-toluenesulfonic acid.
9. The method according to claim 6 or 7, wherein the Schiff base reaction process comprises: under the condition of normal pressure, the wet membrane reacts for 12-24h at 50-60 ℃, then is heated to 80-90 ℃ for reaction for 12-24h, and then is heated to 105-120 ℃ for reaction for 12-24h, so as to obtain the proton exchange membrane.
10. Use of a proton exchange membrane according to any one of claims 1 to 5 in a fuel cell.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112852101A (en) * | 2021-01-22 | 2021-05-28 | 中国石油大学(北京) | Sulfonated polyether ether ketone based proton exchange membrane and preparation method and application thereof |
| CN114373969A (en) * | 2022-01-10 | 2022-04-19 | 中国石油大学(北京) | Composite nanofiber modified proton exchange membrane and preparation method and application thereof |
| CN115181306A (en) * | 2022-08-05 | 2022-10-14 | 吉林省中鼎电力科技发展有限公司 | High-alcohol-resistance and swelling-resistance composite proton exchange membrane and preparation method thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003106515A1 (en) * | 2002-06-14 | 2003-12-24 | ダイキン工業株式会社 | Fluorinated monomer having sulfonate functional group, fluorinated copolymer therefrom and ion exchange membrane |
| AU2004200396A1 (en) * | 1998-08-12 | 2004-02-26 | Thomas Haring | Modification of engineering-polymers with basic N groups and ion-exchange groups in the side chain |
| US20100087553A1 (en) * | 2006-10-17 | 2010-04-08 | Solvay Solexis S.P.A. | Process for stabilizing fluoropolymer having ion exchange groups |
| CN101772534A (en) * | 2007-07-24 | 2010-07-07 | 3M创新有限公司 | Comprise many sulfonic acid polymers and have the cation conductive membranes that contains the anionic metal-salt of F |
| CN101842931A (en) * | 2007-08-29 | 2010-09-22 | 科学与工业研究委员会 | Proton conducting polymer electrolyte membrane useful in polymer electrolyte fuel cells |
| CN104659395A (en) * | 2013-11-20 | 2015-05-27 | 北京迈托科美科技有限公司 | Organic-inorganic composite proton exchange membrane for proton exchange membrane fuel cell and preparation method thereof |
| CN105742678A (en) * | 2016-04-07 | 2016-07-06 | 香港科技大学 | Polymer film applied to redox flow battery and preparation method and application thereof |
| CN106432766A (en) * | 2016-10-09 | 2017-02-22 | 天津大学 | Nafion/orthophosphoric loaded covalent organic framework material composite film, preparation and application |
| CN108199066A (en) * | 2018-01-16 | 2018-06-22 | 成都新柯力化工科技有限公司 | A kind of fuel cell covalent organic framework proton exchange membrane and preparation method |
| CN110137516A (en) * | 2019-05-17 | 2019-08-16 | 华东师范大学 | The sulfur and nitrogen co-doped carbon elctro-catalyst and preparation method of ferro-tin alloy load |
| CN110305347A (en) * | 2019-06-06 | 2019-10-08 | 中国石油大学(北京) | Modified glycan substrate proton exchange and preparation method thereof |
| CN110336052A (en) * | 2019-06-25 | 2019-10-15 | 大连理工大学 | A kind of mixed-matrix type cation-exchange membrane and preparation method thereof |
| CN110380060A (en) * | 2019-07-01 | 2019-10-25 | 江苏乾景新能源产业技术研究院有限公司 | A kind of method for preparing membrane electrode that can improve Proton Exchange Membrane Fuel Cells low humidity runnability |
| CN110684203A (en) * | 2019-10-25 | 2020-01-14 | 南京大学 | Two-dimensional bromine-containing covalent organic framework compound and preparation method thereof |
-
2020
- 2020-11-30 CN CN202011371346.4A patent/CN112510236B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2004200396A1 (en) * | 1998-08-12 | 2004-02-26 | Thomas Haring | Modification of engineering-polymers with basic N groups and ion-exchange groups in the side chain |
| WO2003106515A1 (en) * | 2002-06-14 | 2003-12-24 | ダイキン工業株式会社 | Fluorinated monomer having sulfonate functional group, fluorinated copolymer therefrom and ion exchange membrane |
| US20100087553A1 (en) * | 2006-10-17 | 2010-04-08 | Solvay Solexis S.P.A. | Process for stabilizing fluoropolymer having ion exchange groups |
| CN101772534A (en) * | 2007-07-24 | 2010-07-07 | 3M创新有限公司 | Comprise many sulfonic acid polymers and have the cation conductive membranes that contains the anionic metal-salt of F |
| CN101842931A (en) * | 2007-08-29 | 2010-09-22 | 科学与工业研究委员会 | Proton conducting polymer electrolyte membrane useful in polymer electrolyte fuel cells |
| CN104659395A (en) * | 2013-11-20 | 2015-05-27 | 北京迈托科美科技有限公司 | Organic-inorganic composite proton exchange membrane for proton exchange membrane fuel cell and preparation method thereof |
| CN105742678A (en) * | 2016-04-07 | 2016-07-06 | 香港科技大学 | Polymer film applied to redox flow battery and preparation method and application thereof |
| CN106432766A (en) * | 2016-10-09 | 2017-02-22 | 天津大学 | Nafion/orthophosphoric loaded covalent organic framework material composite film, preparation and application |
| CN108199066A (en) * | 2018-01-16 | 2018-06-22 | 成都新柯力化工科技有限公司 | A kind of fuel cell covalent organic framework proton exchange membrane and preparation method |
| CN110137516A (en) * | 2019-05-17 | 2019-08-16 | 华东师范大学 | The sulfur and nitrogen co-doped carbon elctro-catalyst and preparation method of ferro-tin alloy load |
| CN110305347A (en) * | 2019-06-06 | 2019-10-08 | 中国石油大学(北京) | Modified glycan substrate proton exchange and preparation method thereof |
| CN110336052A (en) * | 2019-06-25 | 2019-10-15 | 大连理工大学 | A kind of mixed-matrix type cation-exchange membrane and preparation method thereof |
| CN110380060A (en) * | 2019-07-01 | 2019-10-25 | 江苏乾景新能源产业技术研究院有限公司 | A kind of method for preparing membrane electrode that can improve Proton Exchange Membrane Fuel Cells low humidity runnability |
| CN110684203A (en) * | 2019-10-25 | 2020-01-14 | 南京大学 | Two-dimensional bromine-containing covalent organic framework compound and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| XINGYUAN WANG等: "In Situ Growth of Cationic Covalent Organic Frameworks (COFs) for Mixed Matrix Membranes with Enhanced Performances", 《LANGMUIR》 * |
| 付凤艳: "离子型聚合物在质子交换膜中的应用", 《化工新型材料》 * |
| 沈文忠: "《太阳能光伏技术与应用》", 31 October 2013 * |
| 金新民: "《主动配电网中的电力电子技术》", 31 January 2015 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112852101A (en) * | 2021-01-22 | 2021-05-28 | 中国石油大学(北京) | Sulfonated polyether ether ketone based proton exchange membrane and preparation method and application thereof |
| CN112852101B (en) * | 2021-01-22 | 2022-04-15 | 中国石油大学(北京) | Sulfonated polyether ether ketone based proton exchange membrane and preparation method and application thereof |
| CN114373969A (en) * | 2022-01-10 | 2022-04-19 | 中国石油大学(北京) | Composite nanofiber modified proton exchange membrane and preparation method and application thereof |
| CN114373969B (en) * | 2022-01-10 | 2023-10-31 | 中国石油大学(北京) | Composite nanofiber modified proton exchange membrane and preparation method and application thereof |
| CN115181306A (en) * | 2022-08-05 | 2022-10-14 | 吉林省中鼎电力科技发展有限公司 | High-alcohol-resistance and swelling-resistance composite proton exchange membrane and preparation method thereof |
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