CN109233274B - Polybenzimidazole membrane with nano porous structure and preparation method thereof - Google Patents
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Abstract
A polybenzimidazole membrane with a nano porous structure and a preparation method thereof belong to the technical field of special polymer functional membranes; adding a filler dispersion liquid into a polybenzimidazole solution, fully mixing, filtering, pouring on a clean glass plate, heating to remove a solvent, and obtaining a polybenzimidazole membrane on the glass plate; and then soaking the nano-porous polybenzimidazole membrane in an etching agent for a certain time, washing the nano-porous polybenzimidazole membrane by using boiling water to remove the residual etching agent, and drying the nano-porous polybenzimidazole membrane to obtain the polybenzimidazole membrane which has high phosphoric acid doping level and high proton conductivity and can be used for high-temperature fuel cells. According to the invention, a ZIFs material with a zeolite imidazole ester framework is used as a pore-forming agent, phosphoric acid is used as an etching agent, a nano-pore structure is formed in situ in the polybenzimidazole membrane, and the ZIFs material can obtain different crystal sizes and morphologies by adjusting the molecular structure of imidazole ligands and the types of metal ions, so that the pore size, the pore morphology, the pore size distribution and the pore connectivity of the prepared porous membrane can be regulated and controlled.
Description
Technical Field
The invention belongs to the technical field of special polymer functional membranes, and particularly relates to a polybenzimidazole membrane with a nano porous structure and a preparation method thereof.
Background
The nano porous polymer membrane has the characteristics of large specific surface area, small density, high stability and good processability, has the dual advantages of porous membranes and polymer materials, and has wide application in the fields of adsorption separation, microreactors, catalyst carriers, sensors and proton exchange membranes of high-temperature fuel cells. However, the porous polymer membrane prepared by the existing method has the problems of wide pore size distribution, uncontrollable pore size, complicated preparation process and environmental pollution caused by discharged waste materials.
Polybenzimidazole is a heterocyclic ladder-shaped polymer containing imidazole groups in main chain repeating units, and has excellent stability, mechanical strength and chemical corrosion resistance. Due to the semi-trapezoidal structure of polybenzimidazole and the existence of imidazole nitrogen atoms in the main chain, the polybenzimidazole belongs to a glassy polymer, the chain rigidity is high, the decomposition temperature can reach 550 ℃, and the main chain contains imidazole groups which can be used as a proton donor and a proton carrier at the same time, so that the polybenzimidazole proton exchange membrane can be widely applied to the field of high-temperature fuel cell proton exchange membranes. Usually, the adsorption capacity and proton conductivity of phosphoric acid are improved by grafting, copolymerization, blending, crosslinking or backbone modification of polybenzimidazole in a manner of introducing sulfonic acid groups or bulky side groups, most of the modification methods are complicated, the improvement of proton conductivity is limited, and the used organic solvent causes pollution to the environment and is not beneficial to industrial application.
The common methods for preparing the porous polymer film at present comprise pore-forming by a pore-forming agent, pore-forming by solvent volatilization, polymer pyrolysis, self-assembly of a segmented copolymer and the like. The porogenic agent has universality, so that the porogenic agent has attracted extensive research interest. However, the polybenzimidazole membrane obtained by using commonly used organic small-molecule pore-forming agents such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diphenyl phthalate, triphenyl phosphate and the like has micron-scale pore size and large pores at high porosity, and the size and distribution of the pores cannot be accurately regulated, so that phosphoric acid is easily rapidly lost when the polybenzimidazole membrane is used as a phosphoric acid-doped proton exchange membrane, and the proton conductivity is reduced.
Therefore, the development of the polybenzimidazole membrane material with a nano-pore structure, adjustable pore diameter, uniform size distribution and simple preparation method has important significance in the field of high-temperature fuel cell proton exchange membranes.
Disclosure of Invention
The invention aims to provide a polybenzimidazole membrane with a nano-porous structure and a preparation method thereof.
The invention relates to a preparation method of a polybenzimidazole membrane with a nano-porous structure, which comprises the following steps:
1) adding the filler dispersion liquid into a polybenzimidazole solution, fully mixing, filtering, pouring on a clean glass plate, heating to remove the solvent, and thus obtaining the polybenzimidazole membrane on the glass plate;
2) soaking the polybenzimidazole membrane obtained in the step 1) in an etching agent for a certain time, then washing with boiling water to remove the residual etching agent, and drying to obtain the polybenzimidazole membrane with the nano-porous structure.
In the above technical solution, the solvent used in the filler dispersion in step 1) is the same as the solvent used in the polybenzimidazole solution, and is one or more of N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and N-methylpyrrolidone (NMP).
In the technical scheme, the filler in the step 1) is a zeolite imidazolate framework material ZIFs series formed by coordination self-assembly of imidazole nitrogen atoms and metals, and comprises ZIF-N nanoparticles (N is 1-100, and N is an integer), the size of the filler is in a nanometer or micrometer scale, the particle size distribution is uniform, the size and the shape of pores of the polybenzimidazole membrane can be regulated and controlled by controlling the size and the shape of the ZIFs nanoparticles, and the pore size can be regulated from the nanometer scale to the micrometer scale.
In the technical scheme, the sum of the mass of the filler and the polybenzimidazole in the step 1) is calculated according to 100%, the mass percentage of the filler is 1-40%, and the balance is the polybenzimidazole; the porosity and the pore communication state of the polybenzimidazole membrane with the nano-porous structure can be regulated and controlled by regulating the dosage ratio of the filler to the polybenzimidazole.
In the above technical solution, the polybenzimidazole in step 1) includes mPBI, OPBI, pPBI, phPBI, SO3PBI、SO2PBI、F6PBI, and the like. The resin is a special high polymer resin with a semi-trapezoidal chemical structure formed by condensation polymerization of a tetrammine monomer and a diacid monomer, and the structural formula of the resin is as follows:
in the technical scheme, in the mixing process of the polybenzimidazole solution and the filler in the step 1), the polybenzimidazole solution and the filler are uniformly dispersed and fully mixed by ultrasonic stirring for 30 min-1 h or at a high speed of 8000-12000 rpm for 30 min-1 h, and the step has important influence on the aperture, the shape and the aperture distribution of the hole in the prepared polybenzimidazole membrane.
In the technical scheme, the method for removing the solvent by heating in the step 1) comprises the steps of drying at 75-85 ℃ for 10-15 hours, drying at 95-105 ℃ for 10-15 hours, drying at 115-125 ℃ for 10-15 hours, and finally vacuumizing and drying at 115-125 ℃ for 10-15 hours.
In the technical scheme, the etching agent in the step 2) is 70-85% (wt) phosphoric acid, the temperature for soaking the polybenzimidazole membrane by the phosphoric acid is 80-200 ℃, and the time for soaking the polybenzimidazole membrane is more than 24 hours.
In the technical scheme, the time for eluting the etching agent by using boiling water in the step 2) is more than 1h until the residual phosphoric acid and part of non-exchanged ions in the film are eluted completely.
In the technical scheme, the steps of etching the filler by using phosphoric acid and eluting the residual phosphoric acid etchant by using boiling water in the step 2) are repeated for more than 2 times until the filler is completely washed away.
According to the invention, a ZIFs material with a zeolite imidazole ester framework is used as a pore-forming agent, phosphoric acid is used as an etching agent, and a nano-pore structure is formed in situ in the polybenzimidazole membrane.
In the invention, because the main chain of the polybenzimidazole contains imidazole groups, each repeating unit contains 2 or more than 2 Lewis basic nitrogen atoms, and the polybenzimidazole can generate acid-base interaction with phosphoric acid molecules to adsorb a large number of phosphoric acid molecules, so that the ZIFs nano particle pore-foaming agent on the surface and in the polybenzimidazole membrane can fully contact with the phosphoric acid to cause the damage of a crystal structure, thereby releasing metal ions and organic micromolecules, and the generated phosphate and the ions and the micromolecules can be treated and exchanged by a large number of phosphoric acid molecules and later-stage boiling water, therefore, the etching agent adopted by the invention is the phosphoric acid. In addition, in proton exchange membrane applications for high temperature fuel cells, phosphoric acid is also the most commonly used proton carrier.
The preparation method of the nano porous polybenzimidazole membrane has the following advantages: (1) the preparation process is simple, the industrialization is easy, an organic solvent is not needed in the pore-forming process, the adopted phosphoric acid etching agent has low cost, the phosphoric acid etching agent is easy to recycle, and the pollutant discharge is reduced; (2) the zeolite imidazole ester framework ZIFs material is adopted, the pore size, the pore morphology and the pore connectivity of the porous membrane can be regulated, and the pore size can be randomly regulated from nano-level to micro-level according to requirements. (3) The polybenzimidazole material is a high-grade engineering plastic, has excellent stability and mechanical strength, the decomposition temperature can reach 550 ℃, and the prepared nano porous structure can keep excellent stability. (4) The polybenzimidazole main chain contains basic groups which can adsorb phosphoric acid, and the nanopore structure introduced by the invention provides a larger internal space, so that the polybenzimidazole has an ultrafast and ultrahigh phosphoric acid adsorption rate and doping level, the pore diameter can be adjusted to be nano-scale, phosphoric acid is not easy to run off, and internal communicating pore channels can store phosphoric acid molecules, so that more free phosphoric acid is introduced, the proton conductivity is improved, and the polybenzimidazole has great application potential in the field of proton exchange membranes of high-temperature fuel cells.
Drawings
FIGS. 1 and 2 are sectional views of the nanoporous polybenzimidazole membrane of example 1 taken by a scanning electron microscope at 30000 and 100000 magnifications.
FIG. 3 is a graph showing the adsorption behavior of phosphoric acid of the mixed matrix membrane ZIF-8/OPBI, the pure OPBI membrane and the porous membrane obtained in example 1 obtained in comparative example 1.
FIG. 4 is a proton conductivity curve of a nanoporous polybenzimidazole membrane (porous OPBI) and a dense polybenzimidazole membrane (OPBI) in example 1 at the same temperature for 24h adsorption of phosphoric acid at 120 ℃.
As shown in fig. 3, the phosphoric acid adsorption behavior curve of the 3 membranes shows that the polybenzimidazole porous membrane reached a phosphoric acid doping level of 28 at 24 hours, which is far superior to that of the dense membrane and the mixed matrix membrane that has not been etched with phosphoric acid, and reached a doping adsorption level of 16 at 1 hour, which shows an ultra-fast phosphoric acid adsorption rate. This is attributed to the fact that the porous structure in the membrane has a larger surface area so that phosphoric acid molecules can be rapidly adsorbed into the membrane, and a large amount of free phosphoric acid can be contained in the pores, thereby improving proton conductivity.
As shown in fig. 4, the proton conductivity of the porous polybenzimidazole membrane obtained by the method of the present invention is much higher than that of an untreated dense polybenzimidazole membrane under the same conditions.
Detailed Description
Example 1
1) Ultrasonically dispersing ZIF-8 nano particles with the size of about 100nm in DMAc, and adding the mixture into a DMAc solution of OPBI, wherein the mass ratio of ZIF-8 to OPBI is 2: and 8, ultrasonically dispersing and violently stirring to uniformly mix the two, filtering impurities by using a 400-mesh filter cloth, casting on a clean glass plate, drying for 12 hours at 80 ℃, 12 hours at 100 ℃, 12 hours at 120 ℃ in a vacuum oven, and finally vacuumizing and keeping the temperature of 120 ℃ for drying for 12 hours to obtain the polybenzimidazole membrane.
2) Soaking the obtained polybenzimidazole membrane in 85% (wt) phosphoric acid at 120 ℃ for 24h, washing with boiling water for 5h to remove residual etchant, and drying at 120 ℃ for 12 h; repeating the washing and drying processes twice to obtain the polybenzimidazole membrane with the nano porous structure.
The polybenzimidazole membrane with a nano-porous structure obtained in the embodiment is characterized by a scanning electron microscope, as shown in fig. 1 and fig. 2, the cross section of the membrane has a porous structure and is a communicating pore channel, and the pore diameter is about 800 nm; as shown in FIGS. 3 and 4, the doping level of phosphoric acid can reach 28 hours at 120 ℃, and the proton conductivity of the 24-hour doped phosphoric acid film is 150mS/cm at 200 ℃.
In the technical scheme, the method for removing the solvent by heating in the step 2) comprises the steps of drying at 75-85 ℃ for 10-15 hours, drying at 95-105 ℃ for 10-15 hours, drying at 115-125 ℃ for 10-15 hours, and finally vacuumizing and drying at 115-125 ℃ for 10-15 hours.
Example 2
1) Ultrasonically dispersing ZIF-8 nano particles with the size of about 150nm in DMAc, and adding the mixture into a DMAc solution of OPBI, wherein the mass ratio of ZIF-8 to OPBI is 2: and 8, ultrasonically dispersing and violently stirring to uniformly mix the two, filtering impurities by using a 400-mesh filter cloth, casting on a clean glass plate, drying for 12 hours at 80 ℃, 12 hours at 100 ℃, 12 hours at 120 ℃ in a vacuum oven, and finally vacuumizing and keeping the temperature of 120 ℃ for drying for 12 hours to obtain the polybenzimidazole membrane.
2) Soaking the obtained polybenzimidazole membrane in 85% (wt) phosphoric acid at 120 ℃ for 12h, washing with boiling water for 5h to remove residual etching agent, and drying at 120 ℃ for 12h to obtain the polybenzimidazole membrane with a nano porous structure, wherein the aperture is about 850 nm. The phosphoric acid doping level can reach 25 in 24 hours under the condition of 120 ℃, and the proton conductivity of the 24-hour doped phosphoric acid film at 200 ℃ is 115 mS/cm.
Example 3
1) Ultrasonically dispersing ZIF-8 nano particles with the size of about 200nm in DMAc, and adding the mixture into a DMAc solution of OPBI, wherein the mass ratio of ZIF-8 to OPBI is 1: and 9, ultrasonically dispersing and violently stirring to uniformly mix the two, filtering impurities by using a filter cloth, casting on a clean glass plate, drying for 12 hours at 80 ℃, drying for 12 hours at 100 ℃, drying for 12 hours at 120 ℃ in a vacuum oven, and finally vacuumizing and keeping the temperature of 120 ℃ for drying for 12 hours to obtain the polybenzimidazole membrane.
2) Soaking the obtained polybenzimidazole membrane in 85% (wt) phosphoric acid at 120 ℃ for 24h, washing with boiling water for 5h to remove residual etching agent, and drying at 120 ℃ for 12h to obtain the polybenzimidazole membrane with a nano porous structure, wherein the aperture is about 750 nm. The phosphoric acid doping level can reach 23 in 24 hours at the temperature of 120 ℃, and the proton conductivity of the 24-hour doped phosphoric acid film at the temperature of 200 ℃ is 100 mS/cm.
Example 4
1) Ultrasonically dispersing ZIF-8 nano particles with the size of about 150nm in DMAc, and adding the mixture into a DMAc solution of OPBI, wherein the mass ratio of ZIF-8 to OPBI is 3: and 7, ultrasonically dispersing and violently stirring to uniformly mix the two, filtering impurities by using a filter cloth, casting on a clean glass plate, drying for 12 hours at 80 ℃, drying for 12 hours at 100 ℃, drying for 12 hours at 120 ℃ in a vacuum oven, and finally vacuumizing and keeping the temperature of 120 ℃ for drying for 12 hours to obtain the polybenzimidazole membrane.
2) Soaking the obtained polybenzimidazole membrane in 85% (wt) phosphoric acid at 120 ℃ for 24h, washing the polybenzimidazole membrane by using boiling water for 5h to remove residual etching agent, and drying the polybenzimidazole membrane at 120 ℃ for 12h to obtain the polybenzimidazole membrane with a nano porous structure, wherein the aperture is about 900nm, the phosphoric acid doping level can reach 25 in 24h at 120 ℃, and the proton conductivity of the polybenzimidazole membrane doped with phosphoric acid at 24h and 200 ℃ is 110 mS/cm.
Example 5
1) Ultrasonically dispersing ZIF-8 nano particles with the size of about 200nm in DMAc, and adding the mixture into a DMAc solution of OPBI, wherein the mass ratio of ZIF-8 to OPBI is 3: and 7, ultrasonically dispersing and violently stirring to uniformly mix the two, filtering impurities by using a filter cloth, casting on a clean glass plate, drying for 12 hours at 80 ℃, drying for 12 hours at 100 ℃, drying for 12 hours at 120 ℃ in a vacuum oven, and finally vacuumizing and keeping the temperature of 120 ℃ for drying for 12 hours to obtain the polybenzimidazole membrane.
2) Soaking the obtained polybenzimidazole membrane in 85% (wt) phosphoric acid at 120 ℃ for 12h, washing with boiling water for 5h to remove residual etching agent, and drying at 120 ℃ for 12h to obtain the polybenzimidazole membrane with a nano porous structure, wherein the aperture is about 1 mu m. The phosphoric acid doping level can reach 28 in 24 hours under the condition of 120 ℃, and the proton conductivity of the 24-hour doped phosphoric acid film at 200 ℃ is 150 mS/cm.
Comparative example 1
Ultrasonically dispersing ZIF-8 nano particles with the size of about 100nm in DMAc, and adding the mixture into a DMAc solution of OPBI, wherein the mass ratio of ZIF-8 to OPBI is 2: and 8, ultrasonically dispersing and violently stirring to uniformly mix the two, filtering impurities by using filter cloth, casting on a clean glass plate, drying for 12 hours at 80 ℃, drying for 12 hours at 100 ℃, drying for 12 hours at 120 ℃ in a vacuum oven, and finally vacuumizing and keeping the temperature of 120 ℃ for drying for 12 hours to obtain the mixed matrix membrane. The doping level of phosphoric acid is 18 at 120 ℃ for 24 hours, and the proton conductivity of the doped phosphoric acid membrane is 80mS/cm at 200 ℃ for 24 hours.
The polybenzimidazole membrane having a nanoporous structure obtained in example 1 and the mixed matrix membrane obtained in comparative example 1 were adsorbed with phosphoric acid at 120 ℃, and the change in the amount of adsorbed phosphoric acid over 24 hours was recorded to obtain the phosphoric acid adsorption behavior graph of fig. 3.
As can be seen from the phosphoric acid adsorption behavior curve of fig. 3, the porous membrane obtained in example 1 exhibits an ultra-fast phosphoric acid adsorption rate and an ultra-high phosphoric acid doping level due to the nano-pore size, and can achieve a high phosphoric acid adsorption amount with an ADL (phosphoric acid doping level) of 16 at 1h, and an ADL of 28 at 24 h. While the adsorption behavior of the ZIF-8/OPBI mixed matrix membrane prepared in comparative example 1 to phosphoric acid was less than ideal.
Therefore, the polybenzimidazole membrane with the nano-porous structure has wide application prospect in the field of proton exchange membranes of high-temperature fuel cells.
Claims (8)
1. A preparation method of a polybenzimidazole membrane with a nano-porous structure comprises the following steps:
1) adding the filler dispersion liquid into a polybenzimidazole solution, fully mixing, filtering, pouring on a clean glass plate, heating to remove the solvent, and obtaining a polybenzimidazole membrane on the glass plate; the filler is one of ZIFs (zero-valent iron) -series ZIF-N nano particles of a zeolite imidazole ester framework material formed by coordination self-assembly of imidazole nitrogen atoms and metal, wherein N is 1-100, and N is an integer; the polybenzimidazole is mPBI, OPBI, pPBI, phPBI, SO3PBI、SO2PBI or F6PBI；
2) Soaking the polybenzimidazole membrane obtained in the step 1) in an etching agent for a certain time, then washing with boiling water to remove the residual etching agent, and drying to obtain the polybenzimidazole membrane with a nano-porous structure; the etching agent is 70-85 wt% phosphoric acid, the temperature for soaking the polybenzimidazole membrane by the phosphoric acid is 80-200 ℃, and the time for soaking the polybenzimidazole membrane is more than 24 hours;
3) the prepared porous polybenzimidazole membrane can be used for a high-temperature proton exchange membrane with high phosphoric acid doping level and high proton conductivity.
2. The method of claim 1, wherein the polybenzimidazole membrane having a nanoporous structure is prepared by: the solvent used by the filler dispersion liquid in the step 1) is the same as that used by the polybenzimidazole solution, and is one or more than two of N, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone.
3. The method of claim 1, wherein the polybenzimidazole membrane having a nanoporous structure is prepared by: in the step 1), the mass sum of the filler and the polybenzimidazole is calculated according to 100%, the mass percentage of the filler is 1-40%, and the balance is the polybenzimidazole.
4. The method of claim 1, wherein the polybenzimidazole membrane having a nanoporous structure is prepared by: and (2) in the mixing process of the polybenzimidazole solution and the filler in the step 1), carrying out ultrasonic stirring for 30 min-1 h or 8000-12000 r/min for 30 min-1 h to uniformly disperse and fully mix the polybenzimidazole solution and the filler.
5. The method of claim 1, wherein the polybenzimidazole membrane having a nanoporous structure is prepared by: the method for removing the solvent by heating in the step 1) comprises the steps of drying at 75-85 ℃ for 10-15 h, drying at 95-105 ℃ for 10-15 h, drying at 115-125 ℃ for 10-15 h, and finally vacuumizing and drying at 115-125 ℃ for 10-15 h.
6. The method of claim 1, wherein the polybenzimidazole membrane having a nanoporous structure is prepared by: the time for eluting the etching agent by boiling water in the step 2) is more than 1h until the residual phosphoric acid and part of the non-exchanged ions in the film are eluted completely.
7. The method of claim 1, wherein the polybenzimidazole membrane having a nanoporous structure is prepared by: repeating the steps of etching the filler with phosphoric acid and eluting the residual phosphoric acid etchant with boiling water in the step 2) for more than 2 times until the filler is completely washed away.
8. A polybenzimidazole membrane with a nanoporous structure characterized by: is prepared by the method of any one of claims 1 to 7.
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| CN113036174B (en) * | 2019-12-09 | 2022-05-31 | 中国科学院大连化学物理研究所 | Organic framework copolymer supported porous ion-conducting membrane and preparation and application thereof |
| CN112259771B (en) * | 2020-09-16 | 2022-02-18 | 深圳大学 | Proton exchange membrane with wide operating temperature, and preparation method and application thereof |
| CN114614060B (en) * | 2022-03-08 | 2023-03-28 | 东北师范大学 | Proton exchange membrane, preparation method and application thereof, and fuel cell comprising proton exchange membrane |
| CN117276611B (en) * | 2023-11-22 | 2024-02-23 | 佛山科学技术学院 | Preparation method of nano hollow polybenzimidazole composite membrane |
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