CN110071313B - Polybenzimidazole multi-component nano high-temperature proton exchange composite membrane, preparation method and application thereof - Google Patents
Polybenzimidazole multi-component nano high-temperature proton exchange composite membrane, preparation method and application thereof Download PDFInfo
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Abstract
A benzimidazolyl multi-component nano high-temperature proton exchange composite membrane, a preparation method and application thereof in a high-temperature proton exchange membrane fuel cell belong to the technical field of high-molecular functional membranes. The invention takes polybenzimidazole as a matrix continuous phase and functional sulfopropylated polysilsesquioxane as a performance enhancing component; by introducing sulfonated polyaryletherketone as a compatibility promoter, the problem that polybenzimidazole is separated out when meeting water in the sol-gel process is effectively solved, and a uniform and stable ternary composite membrane is obtained; the high-temperature proton exchange composite membrane obtained after the ternary composite membrane phosphoric acid is doped has the advantages of good dimensional stability, high proton conductivity, strong acid retention capacity and the like, and is suitable for a membrane electrode assembly process, so that the high-temperature proton exchange composite membrane has great application potential in the field of high-temperature proton exchange membrane fuel cells.
Description
Technical Field
The invention belongs to the technical field of high-molecular functional membranes, and particularly relates to an organic-inorganic enhanced polybenzimidazole multi-component nano high-temperature proton exchange composite membrane containing functional sulfopropylated polysilsesquioxane (SP-POSS), a preparation method and application thereof in a high-temperature proton exchange membrane fuel cell.
Background
The Proton Exchange Membrane Fuel Cell (PEMFC) has the characteristics of high efficiency, environmental protection and the like, and is a real green future energy. Among them, a high temperature proton exchange membrane fuel cell (HT-PEMFC) capable of operating in an environment of 100 to 200 ℃ and no humidity has many incomparable advantages with other types of PEMFCs, such as enhanced tolerance of the catalyst to CO, improved catalyst efficiency, simplified water/thermal management system, etc., and thus is one of the important development directions of automotive power sources in the future. Phosphoric acid doped polybenzimidazole (PA-PBI) type proton exchange membranes were successfully developed in the last 90 s and successfully applied to hydrogen fuel cells. In 2009, the first manned hydrogen fuel cell powered glider successfully tries to fly, and the engine of the airplane is just a PA-PBI-based fuel cell assembly, the operating temperature of the airplane reaches 180 ℃, and the cost can be reduced by 40%. PA-PBI based proton exchange membranes have been the most promising HT-PEM material due to their excellent performance at high temperature operation.
The polymer variety suitable for the high-temperature proton exchange membrane is few, and most researches are limited in a phosphoric acid doped m-PBI system. Because of the molecular structure of m-PBI, the film forming processability of the m-PBI is poor, and although the processing type of the m-PBI can be improved by adopting a low molecular weight polymer, the phosphoric acid doping level and the mechanical strength of the m-PBI are inevitably influenced. Thus, it is necessary to improve the overall performance of these materials by chemically and physically modifying the PBI polymer. The chemical method comprises grafting functional groups on the PBI molecular chain to improve the proton conductivity; the cross-linked PBI membrane has raised mechanical strength and stability, etc. by introducing cross-linkable group. The physical method comprises introducing functional inorganic particles into PBI matrix to improve proton conductivity of the membrane; by introducing the sulfonated polymer into the PBI matrix, the dimensional stability and the like of the composite membrane are improved through the acid-base interaction. A large number of research results show that although the modification methods can improve certain performance of the PA-PBI membrane, other performance of the material is inevitably sacrificed, and thus the application prospect is not optimistic.
It is desirable to incorporate inorganic particles having performance enhancing properties into a polymeric matrix to produce more excellent "organic-inorganic" composites. Although some nano-inorganic particles were successfully doped into the PBI matrix, and have been shown to actually improve the proton conductivity, etc., of the composite membrane. However, it has been found that although these inorganic particles are nano-sized before doping, they inevitably agglomerate after doping a polymer in a certain proportion, resulting in excessively large particle sizes and uneven particle distribution. The sol-gel method adopts a small molecular compound as an additive, so that the small molecular compound is easy to be uniformly dispersed in a polymer solution, and then is dehydrated in a film forming process to form nano particles in a polymer matrix, so that the particles are uniformly distributed, and the size of the particles can be effectively controlled. Therefore, if a method for introducing functional components with the functions of improving proton conductivity, high phosphoric acid adsorption and containing control capacity into a PBI matrix through a sol-gel process can be developed, the method has important significance for the development of the field of preparation of high-temperature proton exchange membranes.
Disclosure of Invention
The invention aims to provide an organic-inorganic enhanced polybenzimidazole based multi-component (PBI/SPAEK/SP-POSS) nano high-temperature proton exchange composite membrane containing functional sulfopropylated polysilsesquioxane (SP-POSS) nano particles and a preparation method thereof.
The invention relates to a preparation method of a polybenzimidazole based multi-component (PBI/SPAEK/SP-POSS) nano high-temperature proton exchange composite membrane, which comprises the following steps:
(1) weighing Polybenzimidazole (PBI) and a compatibility promoter Sulfonated Polyaryletherketone (SPAEK) polymer powder, respectively putting into conical flasks, respectively adding dimethyl sulfoxide (DMSO) or N, N-dimethylacetamide (DMAc) solvents into the conical flasks, and stirring at room temperature to completely dissolve the materials;
(2) slowly dripping 3-trihydroxy silicon-1-propanesulfonic acid (SP-POSS precursor, SP-POSS represents sulfopropylated polysilsesquioxane) water solution into the SPAEK solution obtained in the step (1), dripping 35 wt% of concentrated hydrochloric acid (the volume ratio of the concentrated hydrochloric acid to DMSO or DMAc is 1: 20-200), stirring the solution until the solution is uniformly dissolved, and then performing ultrasonic treatment to uniformly disperse the solution to obtain a transparent SPAEK/SP-POSS mixed solution; wherein the mass fraction of the SP-POSS in the SPAEK matrix is 15-30 wt%;
(3) slowly dripping the SPAEK/SP-POSS mixed solution obtained in the step (2) into the PBI solution obtained in the step (1) while stirring, and ultrasonically treating at room temperature to obtain a uniform and transparent PBI/SPEK/SP-POSS ternary mixed solution; wherein the mass fraction of the SP-POSS in the SPAEK and PBI composite matrix is 1-3 wt%.
(4) Casting the mixed solution obtained in the step (3) on a clean glass plate, drying for 1.5-3.0 hours at 70-90 ℃, and then drying for 20-30 hours at 110-130 ℃; peeling the obtained film from a glass plate, boiling the film for 2 to 5 hours at 100 ℃ by using deionized water, and drying the film for 10 to 20 hours at 110 to 130 ℃ in vacuum to obtain a PBI/SPAEK/SP-POSS ternary composite film;
(5) and (3) immersing the PBI/SPAEK/SP-POSS ternary composite membrane obtained in the step (4) into 80-90 wt% phosphoric acid water solution, and immersing for 72-108 hours at 80-120 ℃ to obtain the polybenzimidazole based multi-component (PBI/SPAEK/SP-POSS) nano high-temperature proton exchange composite membrane.
In the technical scheme, the polybenzimidazole in the step 1) can be soluble PBI such as OPBI and Ph-PBI, preferably Ph-PBI; the structural formula is as follows:
in the technical scheme, the compatibility promoter in the step 1) is SPAEK (including SPEEK, SPEEKK, Ph-SPEEK-co-Ph-SPEEK and the like), preferably Ph-SPEEK-co-Ph-SPEEK; the structural formula is as follows:
in the technical scheme, in the aqueous solution of the 3-trihydroxy silicon-1-propanesulfonic acid (precursor of SP-POSS) in the step 2), the concentration of the 3-trihydroxy silicon-1-propanesulfonic acid is 25-40 wt%.
In the above technical solution, the PBI/SPAEK/SP-POSS mixed solution in step 3) contains water, but is a uniform transparent mixed solution without precipitation.
In the technical scheme, the performance enhancing component in the step 4) is SP-POSS nano particles, 3-trihydroxy silicon-1-propanesulfonic acid is introduced into the high-temperature proton composite membrane in a sol-gel process in a membrane preparation process, and the SP-POSS structure is as follows:
in the technical scheme, the ternary composite membrane can be soaked in a phosphoric acid solution with a certain concentration and a certain temperature to adsorb phosphoric acid, and then a high-temperature proton exchange composite membrane (PA-PBI/SPAEK/SP-POSS) with proton conductivity is obtained.
In the technical scheme, the obtained high-temperature proton exchange composite membrane (PA-PBI/SPAEK/SP-POSS) can be assembled on a membrane electrode and is applied to a high-temperature proton exchange membrane fuel cell.
The invention takes polybenzimidazole as a matrix continuous phase and functional sulfopropylated polysilsesquioxane as a performance enhancing component,by introducing sulfonated polyaryletherketone as a compatibility promoter, the problem of polybenzimidazole precipitation in water in the sol-gel process is effectively solved, and a uniform and stable ternary composite membrane is obtained. The sulfonated polyaryletherketone not only promotes the improvement of the interaction of organic-inorganic phases, but also solves the problem of film formation; it is also possible to use the-SO itself3The H functional group participates in the adsorption and proton conduction of the phosphoric acid molecule; and the stability and the mechanical property of the composite membrane can be improved through the acid-base interaction. Because the material is an ideal material of the proton exchange membrane, the material is essentially different from other coupling agents and surfactants which only play a single function, and has irreplaceable functions. 3-trihydroxy silicon-1-propanesulfonic acid aqueous solution is taken as a raw material, sulfonic acid functionalized SP-POSS nano particles are introduced into a matrix, and the SP-POSS has a large amount of SO on the surface3Inorganic materials with H functional groups, thus having incomparable effect on improving the adsorption and containing control of phosphoric acid (main proton carrier); simultaneous surface SO3The H functional group can also participate in proton conduction, and the surface conduction capability of protons on the nanoparticles is improved.
The polybenzimidazole-based high-temperature proton exchange composite membrane has the following advantages: (1) three components of the composite membrane can participate in proton conduction and generate strong interaction with small molecular phosphoric acid; (2) the nanoparticles carry-SO3H functional group, and adopt sol-gel method to prepare, the organic-inorganic complex film prepared is homogeneous, stable; (3) the composite membrane doped with phosphoric acid has the advantages of good dimensional stability, high proton conductivity, strong acid retention capacity and the like, and can be suitable for a membrane electrode assembly process, so that the composite membrane has great application potential in the field of high-temperature proton exchange membrane fuel cells.
Drawings
FIG. 1 is a photograph of the solutions in comparative example 1 and example 1: in comparative example 1, significant precipitation occurred and film formation could not be achieved; example 1, because SPAEK is introduced, a PBI/SPEK/SP-POSS ternary mixed solution which is transparent is obtained, and the ternary mixed solution can be further cast into a film.
FIG. 2 is a graph of phosphoric acid adsorption (a) versus expansion (b) for a single membrane and a high temperature proton exchange composite membrane; the composite membrane has higher phosphoric acid doping amount and lower size swelling ratio than a single membrane.
FIG. 3 is a graph comparing the phosphoric acid holding capacity of a single membrane with a high temperature proton exchange composite membrane; indicating that the composite membrane has a higher phosphoric acid holding capacity than the single membrane.
FIG. 4 is a graph comparing the cell performance of a high temperature proton exchange composite membrane with that of a single membrane; indicating that the composite membrane has higher single cell electrochemical performance than a single membrane.
As is apparent from the above results, the PBI/SPAEK/SP-POSS composite membrane exhibits higher phosphoric acid doping amount, better dimensional stability, higher proton conductivity, and excellent cell performance, compared to the Ph-PBI single membrane. Therefore, the comprehensive performance of the multi-component nano high-temperature proton exchange composite membrane is obviously improved, and the multi-component nano high-temperature proton exchange composite membrane has practical application potential.
Table 1: comparison of partial Performance data for Single and composite films
Detailed Description
Example 1
1) 0.82g of Ph-PBI and 0.15g of Ph-SPEEK-co-Ph-SPEEK polymer powder were weighed out and put into a conical flask, and 12mL and 3mL of DMSO solutions were added to the conical flask, and stirred at room temperature for 24 hours to dissolve completely. 0.1g of 30 wt% aqueous solution of 3-trishydroxysilane-1-propanesulfonic acid was slowly added dropwise to a Ph-SPEEK-co-Ph-SPEEKK solution, and 0.05mL of concentrated hydrochloric acid (35 wt%) was added dropwise. The solution was stirred for 4 hours to dissolve uniformly, and then the solution was dispersed uniformly by sonication for 1 hour to obtain a transparent SPAEK/SP-POSS mixed solution as shown in FIG. 1 (b).
2) The SPAEK/SP-POSS mixed solution is slowly dripped into the PBI solution while stirring, and ultrasonic treatment is carried out for 2 hours at room temperature to obtain a uniform and transparent PBI/SPAEK/SP-POSS ternary composite solution, as shown in figure 1 (c).
3) The resulting composite solution was cast onto a clean glass plate, dried at 80 ℃ for 2 hours, and then dried at 120 ℃ for 24 hours. The film is peeled off from a glass plate, boiled for 3 hours at 100 ℃ by deionized water and then dried for 12 hours at 120 ℃ in a vacuum oven to obtain a uniform PBI/SPAEK/SP-POSS-3 percent ternary composite film with the thickness of 68 mu m.
Example 2
1) 0.88g of Ph-PBI and 0.10g of Ph-SPEEK-co-Ph-SPEEK polymer powder were weighed out and put into a conical flask, and 12mL and 3mL of DMSO solutions were added to the conical flask, and stirred at room temperature for 24 hours to dissolve completely. 0.067g of 30 wt% aqueous solution of 3-trishydroxysilane-1-propanesulfonic acid was slowly added dropwise to the Ph-SPEEK-co-Ph-SPEEKK solution, and 0.05mL of concentrated hydrochloric acid solution (35 wt%) was added dropwise. The solution is stirred for 4 hours until the solution is uniformly dissolved, and then the solution is uniformly dispersed by ultrasonic treatment for 1 hour to obtain a transparent SPAEK/SP-POSS mixed solution.
2) And slowly dripping the SPAEK/SP-POSS mixed solution into a Ph-PBI solution while stirring, and performing ultrasonic treatment at room temperature for 2 hours to obtain a uniform and transparent PBI/SPAEK/SP-POSS ternary composite solution.
3) The resulting composite solution was cast onto a clean glass plate, dried at 80 ℃ for 2 hours, and then dried at 120 ℃ for 24 hours. The film is peeled off from a glass plate, boiled for 3 hours at 100 ℃ by deionized water and then dried for 12 hours at 120 ℃ in a vacuum oven to obtain a uniform PBI/SPAEK/SP-POSS-2% ternary composite film with the thickness of 65 μm.
Example 3
1) 0.94g of Ph-PBI and 0.05g of Ph-SPEEK-co-Ph-SPEEK polymer powder were weighed out and put into a conical flask, and 12mL and 3mL of DMSO solutions were added to the conical flask, and stirred at room temperature for 24 hours to dissolve completely. 0.034g of 30 wt% aqueous solution of 3-trisilyl-1-propanesulfonic acid was slowly added dropwise to the Ph-SPEEK-co-Ph-SPEEKK solution, and at the same time, 0.05mL of concentrated hydrochloric acid (35%) was added dropwise. The solution is stirred for 4 hours until the solution is uniformly dissolved, and then the solution is uniformly dispersed by ultrasonic treatment for 1 hour to obtain a transparent SPAEK/SP-POSS mixed solution.
2) And slowly dripping the SPAEK/SP-POSS mixed solution into a Ph-PBI solution while stirring, and performing ultrasonic treatment at room temperature for 2 hours to obtain a uniform and transparent PBI/SPAEK/SP-POSS ternary composite solution.
3) The resulting composite solution was cast onto a clean glass plate, dried at 80 ℃ for 2 hours, and then dried at 120 ℃ for 24 hours. The film is peeled off from a glass plate, boiled for 3 hours at 100 ℃ by deionized water and then dried for 12 hours at 120 ℃ in a vacuum oven to obtain a uniform PBI/SPAEK/SP-POSS-1 percent ternary composite film with the thickness of 66 mu m.
Example 4
The above DMSO solvent was replaced by DMAc, and the ternary composite membrane having similar properties was prepared by the same procedure as in examples 1 to 3, except that the weight and ratio of the raw materials were changed.
Example 5
The PBI/SPAEK/SP-POSS-3% composite membrane is soaked in 85 wt% phosphoric acid solution for 72 hours at 120 ℃ to obtain the phosphoric acid doped high-temperature proton exchange composite membrane (PA-PBI/SPAEK/SP-POSS-3%). The phosphoric acid doping level, volume swell and proton conductivity of the composite membrane are listed in table 1.
Example 6
The PBI/SPAEK/SP-POSS-2% composite membrane is soaked in 85 wt% phosphoric acid solution for 72 hours at 120 ℃ to obtain the phosphoric acid doped high-temperature proton exchange composite membrane (PA-PBI/SPAEK/SP-POSS-2%). The phosphoric acid doping level, volume swell and proton conductivity of the composite membrane are listed in table 1.
Example 7
The PBI/SPAEK/SP-POSS-1% composite membrane is soaked in 85 wt% phosphoric acid solution for 72 hours at 120 ℃ to obtain the phosphoric acid doped high-temperature proton exchange composite membrane (PA-PBI/SPAEK/SP-POSS-1%). The phosphoric acid doping level, volume swell and proton conductivity of the composite membrane are listed in table 1.
Example 8
The Ph-PBI single membrane and the high temperature proton exchange composite membrane with different SP-POSS doping amounts were placed in a water vapor atmosphere and the stability of doping acid in the membranes was investigated by recording the change in ADL of each membrane over time. The effect of acid retention capacity is shown in FIG. 3.
Example 9
Phosphoric acid is doped with Ph-And respectively assembling the PBI single membrane and the PA-PBI/SPEEK-SPOSS-1% composite membrane by a membrane electrode. First, polybenzimidazole is dissolved in a mixed solution of formic acid and phosphoric acid to prepare a polymer solution with a mass concentration of 0.5% as a catalyst ink, and a catalyst platinum (Pt) powder is mixed with the prepared catalyst ink so that the mass ratio of the loading amount of platinum to the loading amount of polybenzimidazole in the mixture is 13: 1. the obtained catalyst ink was sprayed onto a gas diffusion layer of a nonwoven fabric to obtain a gas diffusion electrode in which the catalyst Pt was supported in the catalyst layer at a concentration of about 0.6mg/cm2. Hot pressing the phosphoric acid doped polybenzimidazole film between the two gas electrodes (platinum/carbon) to form an electrode/film/electrode sandwich structure, and preparing the test area of 9cm2And a membrane electrode. The cell performance test was conducted in a non-humidified environment at atmospheric pressure at a test temperature of 160 deg.C with dry hydrogen (flow rate 0.3L/min) and oxygen (flow rate 0.15L/min) test gases. The polarization curve and the power density curve are shown in fig. 4.
Comparative example 1
0.82g of Ph-PBI was weighed into a conical flask, and 12mL of DMSO solutions were added to the conical flask, respectively, and stirred at room temperature for 24 hours to dissolve completely. 0.1g of a 30% by mass aqueous solution of 3-trihydroxy silicon-1-propanesulfonic acid was slowly dropped into the solution, and 0.05mL of a concentrated hydrochloric acid solution was simultaneously dropped. It was found that the polymer precipitates to give a non-uniform solution, and even if mechanical stirring and ultrasound were not used, a uniform solution could not be obtained, and a film could not be formed. As shown in fig. 1 (a).
Comparative example 2
1) 0.82g of Ph-PBI polymer powder was weighed into a conical flask, and 12mL of DMSO solutions were added to the conical flask, respectively, and stirred at room temperature for 24 hours to dissolve completely. Then, the mixture was sonicated for 1 hour to obtain a clear PBI/DMSO solution.
2) The resulting composite solution was cast onto a clean glass plate, dried at 80 ℃ for 2 hours, and then dried at 120 ℃ for 24 hours. The film was peeled from the glass plate and deionized water was added at 100 deg.C
After boiling at 3 ℃ for 3 hours, it was dried in a vacuum oven at 120 ℃ for 12 hours to obtain a Ph-PBI single film (thickness 65 μm) as a performance control.
Comparative example 3
The phosphoric acid doping levels, volume swell and proton conductivity after soaking a Ph-PBI single membrane in 85 wt% phosphoric acid solution for 72 hours at 120 ℃ are listed in table 1. The effect of comparing the performance of the Ph-PBI single membrane to the ternary composite membrane is shown in fig. 2, fig. 3, fig. 4 and table 1.
Claims (5)
1. A preparation method of a polybenzimidazole multi-component nano high-temperature proton exchange composite membrane comprises the following steps:
(1) weighing PBI and SPAEK polymer powder as a compatible promoter, respectively putting the PBI and SPAEK polymer powder into a conical flask, respectively adding dimethyl sulfoxide or N, N-dimethylacetamide solvent into the conical flask, and stirring at room temperature to completely dissolve the PBI and SPAEK polymer powder; wherein PBI represents polybenzimidazole, and SPAEK represents sulfonated polyaryletherketone;
(2) slowly dripping 3-trihydroxy silicon-1-propanesulfonic acid aqueous solution into the SPAEK solution obtained in the step (1), and simultaneously dripping 35 wt% of concentrated hydrochloric acid, wherein the volume ratio of the concentrated hydrochloric acid to DMSO or DMAc is 1: 20-200, stirring the solution until the solution is uniformly dissolved, and then performing ultrasonic treatment to uniformly disperse the solution to obtain a transparent SPAEK/SP-POSS mixed solution; wherein the mass fraction of the SP-POSS in the SPAEK matrix is 15-30 wt%; SP-POSS represents sulfopropylated polysilsesquioxane, and 3-trihydroxy silicon-1-propanesulfonic acid aqueous solution is used as a SP-POSS precursor;
(3) slowly dripping the SPAEK/SP-POSS mixed solution obtained in the step (2) into the PBI solution obtained in the step (1) while stirring, and ultrasonically treating at room temperature to obtain a uniform and transparent PBI/SPEK/SP-POSS ternary mixed solution; wherein the mass fraction of the SP-POSS in the SPAEK and PBI composite matrix is 1-3 wt%;
(4) casting the mixed solution obtained in the step (3) on a clean glass plate, drying for 1.5-3.0 hours at 70-90 ℃, and then drying for 20-30 hours at 110-130 ℃; peeling the obtained film from a glass plate, boiling the film for 2 to 5 hours at 100 ℃ by using deionized water, and drying the film for 10 to 20 hours at 110 to 130 ℃ in vacuum to obtain a PBI/SPAEK/SP-POSS ternary composite film;
(5) soaking the PBI/SPAEK/SP-POSS ternary composite membrane obtained in the step (4) into 80-90 wt% phosphoric acid aqueous solution, and soaking at 80-120 ℃ for 72-108 hours to obtain a polybenzimidazole multi-component nano high-temperature proton exchange composite membrane; wherein the polybenzimidazole is OPBI or Ph-PBI, the structural formula is shown as follows,
2. the preparation method of the polybenzimidazole based multi-component nano high-temperature proton exchange composite membrane according to claim 1, which is characterized by comprising the following steps: the compatibility promoter SPAEK polymer is SPEEK, SPEEKK, Ph-SPEEK or Ph-SPEEK-co-Ph-SPEEK, and its structural formula is shown as below,
3. the preparation method of the polybenzimidazole based multi-component nano high-temperature proton exchange composite membrane according to claim 1, which is characterized by comprising the following steps: the structural formula of the SP-POSS is shown as follows,
4. a polybenzimidazole multi-component nano high-temperature proton exchange composite membrane is characterized in that: is prepared by the method of any one of claims 1 to 3.
5. The use of a polybenzimidazole based multi-component nano high temperature proton exchange composite membrane according to claim 4 in a high temperature proton exchange membrane fuel cell.
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