CN113698644A - Cross-linked polybenzimidazole membrane material for high-temperature proton exchange membrane and preparation method thereof - Google Patents
Cross-linked polybenzimidazole membrane material for high-temperature proton exchange membrane and preparation method thereof Download PDFInfo
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- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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Abstract
The invention discloses a cross-linked polybenzimidazole membrane material for a high-temperature proton exchange membrane and a preparation method thereof. The crosslinked polybenzimidazole membrane material is prepared by using linear aryl ether type polybenzimidazole (OPBI) as a raw material and Hexachlorocyclotriphosphazene (HCCP) or imidazole-chlorocyclotriphosphazene (ImCCP) as a crosslinking agent through in-situ covalent crosslinking and membrane formation by a casting method, wherein the imidazole-chlorocyclotriphosphazene is prepared by carrying out nucleophilic substitution reaction on imidazole and hexachlorocyclotriphosphazene. The preparation method has the advantages of simple preparation process and low raw material cost, and the prepared membrane material with the cross-linked structure has the advantages of strong proton conductivity, good chemical stability, excellent battery performance and the like after being doped with phosphoric acid, and has wide application prospect in high-temperature fuel batteries.
Description
Technical Field
The invention belongs to the technical field of high polymer materials and fuel cells, and relates to a material with a cross-linked network structure for a high-temperature proton exchange membrane and a preparation method thereof.
Background
High temperature proton exchange membrane fuel cells (HT-PEMFCs) have the advantages of CO poisoning suppression, simple hydrothermal management, and low dependence on platinum catalysts due to their operating temperatures of 100 ℃ or higher, and thus have attracted much attention as an automatic, stable, and portable clean energy conversion device. Phosphoric Acid (PA) -doped Polybenzimidazole (PBI) membranes, which have been extensively studied, have developed into one of the most promising electrolytes of HT-PEMFCs. PBI-based high temperature PEM fuel cells have several advantages, including high CO or SO2Tolerance, almost anhydrous working conditions and better heat utilization. One of the key issues to achieve superior performance of PBI-based HT-PEMFCs to date is the trade-off between ionic conductivity and mechanical strength. PBI is a class of heterocyclic polymers containing two imidazole groups per repeat unit. These basic groups are easily doped by Phosphoric Acid (PA) molecules. The doping of a large number of PA molecules enables the PBI membrane to have superior proton conductivity. But the doping of PA also reduces the interaction forces between PBI polymer chains, and the mechanical strength of PBI membranes deteriorates drastically with increasing acid doping levels.
Aiming at the defects of the prior art, the polybenzimidazole proton exchange membrane material with a cross-linked structure is prepared by a novel cross-linking agent, and the high-temperature polymer membrane prepared by the method not only has good thermodynamic property, mechanical property and high proton conductivity, but also has stronger phosphoric acid retention rate and excellent dimensional stability.
Disclosure of Invention
The invention aims to provide a novel cross-linked polybenzimidazole membrane material for a high-temperature proton exchange membrane, which has a good application prospect in the field of high-temperature proton exchange membrane fuel cells.
The invention also aims to provide a preparation method of the cross-linked polybenzimidazole membrane material.
The invention also aims to provide the application of the cross-linked polybenzimidazole membrane material in a high-temperature proton exchange membrane fuel cell.
A cross-linked polybenzimidazole membrane material for a high-temperature proton exchange membrane has the following structure:
wherein X is OPBI or
OPBI of
The preparation method of the crosslinked polybenzimidazole membrane material for the high-temperature proton exchange membrane is obtained by using polybenzimidazole (OPBI) as a raw material and hexachlorocyclotriphosphazene or imidazole-chlorocyclotriphosphazene as a crosslinking agent and performing in-situ covalent crosslinking to form a membrane by a casting method.
Preferably, in the above preparation method, the imidazole-chlorocyclotriphosphazene is obtained by nucleophilic substitution reaction (1-4 chlorine is substituted) of imidazole and hexachlorocyclotriphosphazene, and the structure is selected from the following:
preferably, in the above preparation method, the degree of crosslinking is controlled by adjusting the ratio of polybenzimidazole to hexachlorocyclotriphosphazene or imidazole-chlorocyclotriphosphazene so that the degree of reactivity of imidazole groups in polybenzimidazole is 10 to 30%.
Preferably, in the preparation method, polybenzimidazole and hexachlorocyclotriphosphazene or imidazole-chlorocyclotriphosphazene are respectively dissolved in a polar aprotic solvent, the two solutions are mixed and stirred uniformly, then a film is formed by a solution casting method, and-Cl and imidazole carry out in-situ nucleophilic substitution reaction in the process of evaporating the solvent, so that crosslinking is carried out, and the crosslinked polybenzimidazole film material is obtained.
Preferably, in the above preparation method, the polar aprotic solvent is one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, or dimethylsulfoxide.
Preferably, in the above preparation method, the temperature of the evaporated solvent is controlled in a gradient manner, and the solvent is kept at 60 to 80 ℃ for 5 to 12 hours and at 130 to 150 ℃ for 2 to 6 hours to allow sufficient crosslinking.
Preferably, in the above preparation method, the preparation method of imidazole-chlorocyclotriphosphazene comprises the following steps:
(1) adding hexachlorocyclotriphosphazene into a polar organic solvent, stirring and dissolving to obtain a transparent and uniform solution for later use;
(2) adding imidazole into a polar organic solvent, stirring and dissolving to obtain a transparent and uniform solution for later use;
(3) and (3) adding the imidazole solution into the hexachlorocyclotriphosphazene solution at the temperature of 25-70 ℃ to prepare the imidazole-chlorocyclotriphosphazene solution.
Preferably, in the above preparation method, the molar ratio of the imidazole to the hexachlorocyclotriphosphazene is 1-4: 1.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, a cross-linked structure is introduced into the polybenzimidazole membrane through covalent cross-linking modification, so that the mechanical property and the dimensional stability of the membrane are greatly improved; due to the increase of the doping amount of the phosphoric acid per unit volume, the proton conductivity is also improved.
2. The novel cross-linking agent is suitable for batch production, the cross-linking process is very simple, the novel cross-linking agent is suitable for large-scale industrial production, and the prepared cross-linked polybenzimidazole high-temperature proton exchange membrane has excellent performance when being applied to a high-temperature fuel cell.
Drawings
FIG. 1 shows proton conductivities of polybenzimidazole high-temperature proton exchange membrane materials with cross-linked network structures prepared in examples 1 to 4 and commercial polybenzimidazole membranes at a temperature of 80 to 160 ℃ without humidification.
FIG. 2 is H at 160 ℃ without humidification of a high temperature proton exchange membrane material of a cross-linked network structure prepared in example 4 and a commercial polybenzimidazole membrane2/O2Battery performance is plotted.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1: the preparation method of the PBI-HCCP-10% high-temperature proton exchange membrane material comprises the following steps:
adding polybenzimidazole resin into an N-methylpyrrolidone solution, heating and stirring to dissolve the polybenzimidazole resin to obtain a macromolecular solution with the mass fraction of 5 wt%; adding hexachlorocyclotriphosphazene into the N-methylpyrrolidone solution, and stirring to dissolve the hexachlorocyclotriphosphazene to obtain a solution with the mass fraction of 1 wt%; controlling the molar ratio of hexachlorocyclotriphosphazene to imidazole ring in polybenzimidazole to be 1: 60, namely, 10 percent of imidazole rings are subjected to nucleophilic substitution reaction; dropwise adding the hexachlorocyclotriphosphazene solution into the polybenzimidazole solution to finally obtain a uniform solution containing the cross-linking agent; and (2) adopting a solution casting film-forming method, casting a uniform solution containing a cross-linking agent on a glass plate, heating for 10 hours at 80 ℃, heating for 3 hours at 150 ℃, volatilizing to remove a solvent to obtain a cross-linked polybenzimidazole film material, soaking the cross-linked film in 85 wt% phosphoric acid at 120 ℃ for 12 hours, and taking out to obtain the required cross-linked high-temperature proton exchange film.
Example 2: the preparation method of the PBI-HCCP-20% high-temperature proton exchange membrane material comprises the following steps:
adding polybenzimidazole resin into an N-methylpyrrolidone solution, heating and stirring to dissolve the polybenzimidazole resin to obtain a macromolecular solution with the mass fraction of 5 wt%; adding hexachlorocyclotriphosphazene into the N-methylpyrrolidone solution, and stirring to dissolve the hexachlorocyclotriphosphazene to obtain a solution with the mass fraction of 1 wt%; controlling the molar ratio of hexachlorocyclotriphosphazene to imidazole ring in polybenzimidazole to be 1: 30, namely, 20 percent of imidazole rings are subjected to nucleophilic substitution reaction; dropwise adding the hexachlorocyclotriphosphazene solution into the polybenzimidazole solution to obtain a uniform solution containing the cross-linking agent; and (2) adopting a solution casting film-forming method, casting a uniform solution containing a cross-linking agent on a glass plate, heating for 10 hours at 80 ℃, heating for 3 hours at 150 ℃, volatilizing to remove a solvent to obtain a cross-linked polybenzimidazole film material, soaking the cross-linked film in 85 wt% phosphoric acid at 120 ℃ for 12 hours, and taking out to obtain the required cross-linked high-temperature proton exchange film.
Example 3: the preparation method of the PBI-ImCCP-10% high-temperature proton exchange membrane material comprises the following steps:
adding polybenzimidazole resin into an N-methylpyrrolidone solution, heating and stirring to dissolve the polybenzimidazole resin to obtain a macromolecular solution with the mass fraction of 5 wt%; adding hexachlorocyclotriphosphazene into the N-methylpyrrolidone solution, and stirring to dissolve the hexachlorocyclotriphosphazene to obtain a solution with the mass fraction of 2 wt%; adding imidazole into an N-methylpyrrolidone solution, and stirring to dissolve the imidazole to obtain a solution with the mass fraction of 2 wt%; dripping 3g of imidazole solution into 5.1g of hexachlorocyclotriphosphazene solution at the temperature of 30 ℃, and continuously stirring for 30min after dripping to prepare imidazole-chlorocyclotriphosphazene solution; controlling the molar ratio of-Cl in the imidazole-chloro cyclotriphosphazene to imidazole ring in the polybenzimidazole to be 1: 10, namely, 10 percent of imidazole rings are subjected to nucleophilic substitution reaction; then dripping the imidazole-chlorocyclotriphosphazene solution into the polybenzimidazole solution to finally obtain a uniform proton exchange membrane solution containing the cross-linking agent; and adopting a solution casting film-forming method, casting a uniform solution containing a cross-linking agent on a glass plate, heating for 10 hours at 80 ℃, heating for 3 hours at 150 ℃, volatilizing to remove a solvent to obtain a cross-linked polybenzimidazole film material, soaking in 85 wt% phosphoric acid at 120 ℃ for 12 hours, and taking out to obtain the required cross-linked high-temperature proton exchange membrane.
Example 4: the preparation method of the PBI-ImCCP-20% high-temperature proton exchange membrane material comprises the following steps:
adding polybenzimidazole resin into an N-methylpyrrolidone solution, heating and stirring to dissolve the polybenzimidazole resin to obtain a macromolecular solution with the mass fraction of 5 wt%; adding hexachlorocyclotriphosphazene into the N-methylpyrrolidone solution, and stirring to dissolve the hexachlorocyclotriphosphazene to obtain a solution with the mass fraction of 2 wt%; adding imidazole into an N-methylpyrrolidone solution, and stirring to dissolve the imidazole to obtain a solution with the mass fraction of 2 wt%; 3g of imidazole solution was added dropwise to 5.1g at 30 deg.CContinuously stirring for 30min after the dropwise addition of the hexachlorocyclotriphosphazene solution to prepare an imidazole-chlorocyclotriphosphazene solution; controlling the molar ratio of-Cl in the imidazole-chloro cyclotriphosphazene to imidazole ring in the polybenzimidazole to be 1: 5, that is, nucleophilic substitution reaction occurs on 20 percent of imidazole rings; then dripping the imidazole-chlorocyclotriphosphazene solution into the polybenzimidazole solution to finally obtain a uniform proton exchange membrane solution containing the cross-linking agent; and adopting a solution casting film-forming method, casting a uniform solution containing a cross-linking agent on a glass plate, heating for 10 hours at 80 ℃, heating for 3 hours at 150 ℃, volatilizing to remove a solvent to obtain a cross-linked polybenzimidazole film material, soaking in 85 wt% phosphoric acid at 120 ℃ for 12 hours, and taking out to obtain the required cross-linked high-temperature proton exchange membrane. H of the obtained high-temperature proton exchange membrane material and commercial polybenzimidazole membrane under the condition of no humidification at 160 DEG C2/O2The battery performance ratio is shown in fig. 2.
Claims (9)
1. A cross-linked polybenzimidazole membrane material for a high-temperature proton exchange membrane is characterized by having the following structure:
wherein X is OPBI or
OPBI of
2. The method for preparing a cross-linked polybenzimidazole membrane material for a high-temperature proton exchange membrane according to claim 1, which is characterized in that polybenzimidazole (OPBI) is used as a raw material, hexachlorocyclotriphosphazene or imidazole-chlorocyclotriphosphazene is used as a cross-linking agent, and the material is obtained by in-situ covalent cross-linking and membrane forming through a casting method.
3. The method of claim 2, wherein the imidazole-chlorocyclotriphosphazene is obtained by nucleophilic substitution reaction (1-4 chlorine displacement) of imidazole and hexachlorocyclotriphosphazene, and has a structure selected from the group consisting of:
a
b
c
d
e
f
g
4. the method according to claim 2, wherein the degree of crosslinking is controlled by adjusting the ratio of polybenzimidazole to hexachlorocyclotriphosphazene or imidazole-chlorocyclotriphosphazene so that the degree of reactivity of imidazole groups in polybenzimidazole is 10 to 30%.
5. The preparation method according to claim 2, wherein polybenzimidazole and hexachlorocyclotriphosphazene or imidazole-chlorocyclotriphosphazene are respectively dissolved in polar aprotic solvent, the two solutions are mixed and stirred uniformly, then a film is formed by a solution casting method, and-Cl and imidazole carry out in-situ nucleophilic substitution reaction in the process of solvent evaporation, so that crosslinking is carried out, and the crosslinked polybenzimidazole film material is obtained.
6. The method of claim 2, wherein the polar aprotic solvent is one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, or dimethylsulfoxide.
7. The method according to claim 2, wherein the temperature of the solvent is controlled in a gradient manner, and the solvent is maintained at 60 to 80 ℃ for 5 to 12 hours and at 130 to 150 ℃ for 2 to 6 hours to allow sufficient crosslinking.
8. The method of claim 2, wherein the imidazole-chlorocyclotriphosphazene is prepared by the steps of:
(1) adding hexachlorocyclotriphosphazene into a polar organic solvent, stirring and dissolving to obtain a transparent and uniform solution for later use;
(2) adding imidazole into a polar organic solvent, stirring and dissolving to obtain a transparent and uniform solution for later use;
(3) and (3) adding the imidazole solution into the hexachlorocyclotriphosphazene solution at the temperature of 25-70 ℃ to prepare the imidazole-chlorocyclotriphosphazene solution.
9. The method of claim 8, wherein the molar ratio of imidazole to hexachlorocyclotriphosphazene is 1-4: 1.
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| US20190169372A1 (en) * | 2016-08-04 | 2019-06-06 | Simon Fraser University | Crosslinking of Hydroxide Stable, Polybenzimidazoliums and Polyimidazoliums Membranes and Ionomers |
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