CN115020771A - HBM blending modification-based PBI proton exchange membrane and preparation method and application thereof - Google Patents
HBM blending modification-based PBI proton exchange membrane and preparation method and application thereof Download PDFInfo
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- CN115020771A CN115020771A CN202210493112.XA CN202210493112A CN115020771A CN 115020771 A CN115020771 A CN 115020771A CN 202210493112 A CN202210493112 A CN 202210493112A CN 115020771 A CN115020771 A CN 115020771A
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 229920000642 polymer Polymers 0.000 description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- 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]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a PBI proton exchange membrane based on HBM blending modification and a preparation method and application thereof, belonging to the field of fuel cells. The method comprises the following steps: mixing p-diaminobenzene sulfonic acid and trimesic acid in proportion, adding pyridine, N-methyl pyrrolidone, triphenyl phosphite and anhydrous LiCl for polymerization reaction, and performing post-treatment to obtain brown-yellow HBM; and then blending HBM and PBI, and obtaining the modified PBI proton exchange membrane by a solution casting method. The HBM synthesized by the invention can establish effective proton transmission channel by the intermolecular and intramolecular hydrogen bond effect, and-NH 3 The end-capped HBM molecules can better anchor phosphoric acid in the PBI to enable the PBI not to be easily lost, and a large number of sulfonic acid groups are introduced, so that the proton exchange efficiency is increased, and the proton conductivity of the PBI membrane is improved. The conductivity of the PBI proton exchange membrane modified by the blending method at high temperature is improved, and the attenuation of the proton conductivity of the modified PBI proton exchange membrane is greatly slowed down after the modified PBI proton exchange membrane is continuously tested at 180 ℃ for 100 hours.
Description
Technical Field
The invention belongs to the technical field of fuel cells, particularly relates to a proton exchange membrane material, and more particularly relates to a sulfonated hyperbranched macromolecule (HBM) -based blending modified Polybenzimidazole (PBI) proton exchange membrane, and a preparation method and application thereof.
Background
The environmental pollution and energy shortage problem still remain the urgent problem to be solved in the world, and Proton Exchange Membrane Fuel Cell (PEMFC) is one of the most promising clean energy devices, which has high mass and volume specific power density, high energy conversion efficiency, and almost zero emission in the case of pure hydrogen as fuel, and is environmentally friendly.
However, when the PEMFC is operated at a temperature below 100 ℃, problems may occur, for example, when the temperature is low, the catalytic activity of the electrode reaction is low, impurities in the fuel may cause catalyst poisoning, gas-liquid two phases coexist in the cell, the mass transfer control is complex, the hydrothermal management is complex, and the cost is high. In response to these problems, the choice of PEMFCs that operate at high temperatures (100 ℃ to 200 ℃) is an effective solution. However, the proton conductivity of the conventional Nafion membrane is rapidly reduced in a high-temperature and low-humidity environment, and the performance is seriously damaged, so that the development of a high-temperature proton exchange membrane fuel cell is critical to the development of a high-temperature proton exchange membrane (HTPEM).
In order for PEMFCs to function properly under high-temperature conditions, HTPEM materials need to satisfy the following conditions: high proton conductivity at high temperature, excellent mechanical property, good chemical stability, good thermal stability, long service life and the like. Polybenzimidazole (PBI) becomes the most concerned high-temperature proton exchange membrane material at present due to the characteristics of high glass transition temperature, good thermal stability, high mechanical strength and the like. The electrochemical performance of PBI is extremely low, and doped Phosphoric Acid (PA) is required to be used as a Proton Exchange Membrane (PEM), but the application of the PBI membrane is limited by the problems of PA-PBI. On one hand, if the doping content of PA is too low, the proton conductivity of the PBI membrane is poor; the mechanical properties of the PBI film are severely degraded when the PA content is high. On the other hand, under the working condition of high temperature (100 ℃ to 200 ℃), the phosphoric acid doped in the membrane is easy to run off, and the running-off phosphoric acid not only can reduce the proton conductivity of the proton exchange membrane, but also can poison the catalyst and corrode other parts of the battery, so that the performance and the service life of the fuel battery are seriously damaged.
Disclosure of Invention
In view of this, the invention aims to provide a sulfonated hyperbranched macromolecule (HBM) -based blend modified Polybenzimidazole (PBI) proton exchange membrane, and a preparation method and an application thereof, so as to solve the defects of a PA-doped PBI proton exchange membrane in the prior art.
In order to achieve the above object of the present invention:
in a first aspect, the invention provides a method for blending and modifying a Polybenzimidazole (PBI) proton exchange membrane based on a sulfonated hyperbranched macromolecule (HBM), comprising the following steps:
s1: mixing p-Diaminobenzene Sulfonic Acid (DSA) and Trimesic Acid (TA) according to a certain proportion, then adding a certain amount of pyridine, N-methyl pyrrolidone, triphenyl phosphite and anhydrous LiCl, and carrying out polymerization reaction on the obtained mixed solution under the condition of inert atmosphere; after the reaction is finished, washing and suction filtering are carried out, then the sulfonated hyperbranched macromolecule (HBM) with brown yellow color is obtained after NaOH solution treatment and vacuum drying;
s2: blending the HBM prepared in the step S1 and Polybenzimidazole (PBI) in an organic solvent, and obtaining a modified PBI proton exchange membrane by a solution casting method, namely the HBM blending-based modified PBI proton exchange membrane.
Further, the predetermined ratio in step S1 means that the molar ratio of DSA to TA is 2 or more and less than 3. For example, the molar ratio of DSA to TA may be 9: 4. 21: 10...2: 1, etc. The invention is characterized in that the molar ratio of DSA to TA is more than or equal to 3: 4. and less than 1: the carboxyl-terminated HBM is produced at 1.
Optionally, the total mass of DSA and TA in step S1 is 1-1.5 g.
Alternatively, the amounts stated in step S1 were 3ml of pyridine, 4ml of N-methylpyrrolidone, 1ml of triphenyl phosphite, and 0.4g of anhydrous LiCl.
Optionally, in the polymerization reaction described in step S1, the reaction conditions are: the reaction temperature is 100 ℃, and the reaction time is 0.5-2 h. The reaction time is determined according to the degree of polymerization, and the mixed solution is changed into a solid state within a certain period of time within 0.5-2 hours generally, so that the polymerization is completed. Different reaction times had no effect on the product.
Further, the inert atmosphere in step S1 is an argon atmosphere or a nitrogen atmosphere.
Alternatively, in the washing operation of step S1, the washing is performed with anhydrous methanol and with suction filtration three times, and then with deionized water and with suction filtration three times.
Further, the concentration of the NaOH solution used in step S1 was 1mol/L, and the brown powder was sufficiently stirred in the NaOH solution for 12 hours.
Further, the temperature was set to 100 ℃ in the vacuum drying operation at step S1, and the drying time was 12 hours.
Further, in step S2, the organic solvent used for blending HBM and PBI is dimethyl sulfoxide (DMSO) or Dimethylformamide (DMF).
Alternatively, the blending in step S2 is well stirred at 100 ℃ for 48 h.
Optionally, in step S2, when blending with the PBI, the mass fraction of the HBM in the total mass of the HBM and the PBI is 2.5 to 7.5%, and more preferably 2.5 to 5%.
Further, the blend of HBM and PBI was uniformly cast on a glass plate and dried on a hot plate at 80 ℃ for 2 hours.
In a second aspect, the invention also provides an HBM blending modification-based PBI proton exchange membrane prepared by the method.
In a third aspect, the invention also provides an application of the PBI proton exchange membrane based on HBM blending modification in a fuel cell.
A fuel cell comprises the HBM blending modified PBI proton exchange membrane.
Compared with the prior art, the PBI proton exchange membrane based on HBM blending modification and the preparation method and the application thereof have the following beneficial effects:
in the invention, the sulfonated hyperbranched macromolecule terminated by amino is synthesized by the p-diaminobenzene sulfonic acid and the trimesic acid with specific proportion, and the polymer has a large number of sulfonic acid groups in the molecule, so that HBM has excellent proton transmission efficiency. Because HBM is amino-terminated, the end-capping group on the outermost layer of the molecule is-NH 3 And thus more phosphate molecules can be anchored. HBM has good thermal stability, completely meets the working condition of a high-temperature fuel cell, is introduced into a PBI matrix, and realizes good dispersibility and proton channel creation by establishing a hydrogen bond network between PBI and HBM. The PBI proton exchange membrane obtained by blending modification is high in density of sulfonate and large in amount of-NH 3 The introduction of the group greatly improves the proton transmission efficiency and the proton conductivity of the PBI membrane: the conductivity of the PBI proton exchange membrane modified by the blending method of the invention at high temperature (110-180 ℃) is higher than that of the unmodified PBI membrane, and the attenuation of the proton conductivity of the modified PBI membrane is greatly slowed down after the PBI membrane is continuously tested at 180 ℃ for 100 h. And, due to the hyperbranched structure of HBM and-NH 3 The groups can anchor PA molecules better, and the phosphoric acid loss of the PBI membrane at high temperature is slowed down.
Drawings
FIG. 1 is a synthesis scheme of HBM synthesized in step S1 of example 1 of the present invention and HBM of comparative example 1;
FIG. 2 is a process flow diagram of the sulfonated hyperbranched macromolecule-based blend modified PBI proton exchange membrane of the present invention;
FIG. 3 is a Nuclear Magnetic Resonance (NMR) spectrum of an amino terminated HBM in example 1 of the present invention and a carboxyl terminated HBM in comparative example 1;
FIG. 4 is a graph of the infrared spectrum (FTIR) of an amino terminated HBM in example 1 of the invention versus a carboxy terminated HBM in comparative example 1;
FIG. 5 is a graph of the infrared spectrum (FTIR) of a modified PBI membrane compared to an unmodified PBI membrane in examples 1-3 of the present invention;
FIG. 6 is an X-ray diffraction pattern (XRD) of a modified PBI membrane in examples 1-3 of the present invention versus an unmodified PBI membrane;
FIG. 7 is a Scanning Electron Microscope (SEM) image of the plane and cross-section of the modified PBI membrane and the unmodified PBI membrane in examples 1-3 of the present invention.
FIG. 8 is a 3D phase diagram of the modified PBI film under Atomic Force Microscope (AFM) in examples 1-3 of the present invention;
FIG. 9 is a graph showing the thermogravimetric curves of the modified PBI membranes in examples 1-3 of the present invention compared to the unmodified PBI membranes;
FIG. 10 is a graph showing the results of a volume swell ratio test in PA and a PA doping ratio test in examples 1 to 3 of the present invention for a modified PBI membrane in comparison with an unmodified PBI membrane;
FIG. 11 is a graph of the electrical conductivity of the modified PBI membrane and the unmodified PBI membrane of examples 1 to 3 of the present invention at a temperature of 110 ℃ to 180 ℃;
FIG. 12 is a proton conductivity graph of the modified PBI membrane and the unmodified PBI membrane of examples 1 to 3 of the present invention operated at 180 ℃ for a long time.
Detailed Description
The objects, technical solutions and advantages of the present invention will be more clearly and completely described in the following with reference to the embodiments of the present invention.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless otherwise indicated, the numerical parameters set forth in the specification are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The equipment and raw materials used in the present invention are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
As shown in fig. 1, the preparation method of the HBM blend modified PBI proton exchange membrane (PBI-HBM 5%) of the present invention comprises the following steps:
s1: mixing p-Diaminobenzene Sulfonic Acid (DSA) and Trimesic Acid (TA) according to a certain proportion, then adding a certain amount of pyridine, N-methyl pyrrolidone, triphenyl phosphite and anhydrous LiCl, and carrying out polymerization reaction on the obtained mixed solution under the condition of inert atmosphere; after the reaction is finished, washing and suction filtering are carried out, then the sulfonated hyperbranched macromolecule (HBM) with brown yellow color is obtained after NaOH solution treatment and vacuum drying; wherein:
s2: blending the HBM prepared in the step S1 and Polybenzimidazole (PBI) in an organic solvent, and obtaining a modified PBI proton exchange membrane by a solution casting method, namely the HBM blending-based modified PBI proton exchange membrane.
The structural formula of the p-Diaminobenzene Sulfonic Acid (DSA) is shown as the following formula I:
the structural formula of the Trimesic Acid (TA) is shown as the following formula II:
in the embodiment of the application, p-diaminobenzene sulfonic acid and trimesic acid are blended in a double-neck flask, then the double-neck flask is ventilated for three times and then is introduced with inert atmosphere, then a syringe is used for adding 3ml of pyridine, 4ml of N-methyl pyrrolidone and 1ml of triphenyl phosphite into the double-neck flask, and the mixture is stirred for 0.5-2 hours at the temperature of 100 ℃. After the reaction is finished, the obtained solid is crushed, washed with anhydrous methanol and deionized water for three times respectively, and filtered, and then the sulfonated hyperbranched macromolecule (HBM) is obtained. In order to make HBM blend better with PBI, HBM was stirred in 1mol/l sodium hydroxide solution for 12h to neutralize the acidic groups in HBM. The HBM was then dried in a vacuum oven at 100 ℃ for 12h to completely remove residual solvent and water from the HBM, resulting in a tan HBM particle.
In the examples of the application, the dosage of the diaminobenzene sulfonic acid is 0.8g, the dosage of the trimesic acid is 0.447g, and the molar ratio is DSA (molar ratio of TA to TA of 2: 1.
in the examples of the present application, the inert gas atmosphere used was an argon gas atmosphere.
In the application example, 20mg of the brown yellow particles HBM and 380mg of PBI powder are dissolved and blended in 5ml of dimethyl sulfoxide under stirring, the temperature is set to be 100 ℃, and the time is 48 hours. After blending, the mixed solution is cast on a glass plate, a film pusher is adjusted to 60 mu m to push the solution flat, and the solution is placed on a heating plate, the temperature is set to 80 ℃, and the drying time is 2 h. Finally obtaining the modified PBI proton exchange membrane with the thickness of about 40 mu m, wherein the mass fraction of HBM is 5%.
In the examples of the present application, a sulfonated polymer is first produced by polymerization of Diaminobenzene Sulfonic Acid (DSA) and Trimesic Acid (TA), and since DSA is in excess compared to TA, the outermost layer of the hyperbranched molecular structure of the polymer is composed of-NH 3 The end capping is carried out on the groups, and sulfonate exists in DSA molecules, so that a large amount of sulfonate in HBM can greatly improve proton transmission efficiency. It is due to the large amount of sulfonate and-NH in HBM molecule 3 The group improves the proton conductivity of the membrane after the group is mixed with PBI, and reduces the loss of phosphoric acid in a working state. Because of the excellent electrochemical performance of the polymer HBM, the polymer HBM is blended with the modified PBI membrane, the problems of insufficient PA doping and easy loss of PA of the traditional PBI membrane are solved, and finally the high proton conductivity and low PA loss rate of the modified PBI membrane at high temperature are realized, so that the polymer HBM has a good application prospect.
Based on the same inventive concept, the embodiment of the application also provides the PBI proton exchange membrane modified based on the HBM blending, and the PBI proton exchange membrane is prepared by adopting the preparation method.
Based on the same inventive concept, the embodiment of the application also provides the application of the HBM blending modified PBI proton exchange membrane in a fuel cell.
Comparative example 1
This comparative example is substantially the same as example 1 except that the molar ratio of DSA to TA in step S1 of this comparative example is 9:10 and no treatment with a sodium hydroxide solution is carried out after washing with suction filtration.
Example 2(PBI-HBM 2.5%)
The difference from example 1 is that the amount of HBM added in this example is 2.5% of the total amount of HBM and PBI.
Example 3(PBI-HBM 7.5%)
The difference from example 1 is that the amount of HBM added in this example is 7.5% of the total amount of HBM and PBI.
And (3) performance characterization:
as shown in FIG. 1, the carboxyl group (-COOH) on TA and the amino group (-NH) on DSA 2 ) Amide bonds are formed by dehydration condensation. Theoretically, three DSA molecules and one TA molecule can form a macromolecule with the TA molecule as the center and three amino groups on the outermost layer. Therefore, when the molar ratio of DSA to TA is less than 3 and 2 or more, a polymer having amino groups in the outermost layer is formed, and the polymerization degree of HBM obtained becomes higher as the ratio becomes closer to 2:1 (when the molar ratio of DSA to TA is 3: 1, the polymerization degree of the product becomes insufficient, and the reaction solution cannot be polymerized into a solid state, and therefore, this ratio is not included). Similarly, when the molar ratio of DSA to TA is more than 3: 4 is less than 1: 1, a carboxyl terminated HBM is formed. Since the amino-terminated HBMs of different degrees of polymerization are structurally similar and in too many proportions, only HBMs of one degree of polymerization (i.e., a DSA to TA molar ratio of 2: 1) are selected in the present invention and HBMs of other degrees of polymerization are not discussed.
In the synthesis of HBM, when trimesic acid is in excess, a carboxyl-terminated product is produced, and in the present invention, since the produced HBM is amino-terminated because of DSA: TA ═ 2: 1. As in fig. 3, two sets of characteristic absorption peaks at chemical shifts a of 11.8ppm and b of 10.9ppm are signals of hydrogen atoms of the end-capped carboxyl groups of the sulfonated hyperbranched macromolecular polymer, and the disappearance of these two signals in the amino-terminated HBM can preliminarily confirm the successful synthesis of the amino-terminated HBM. The disappearance of the characteristic absorption peak in the chemical shift a of 7-9 ppm may be caused by the disappearance of the hydrogen atom signal in the sulfonate group due to the treatment of the sodium hydroxide solution when the amino-terminated HBM is treated.
As shown in FIG. 4, the infrared spectrum curve is 1745cm -1 And 1450cm -1 The characteristic peaks at (a) are, in order, stretching vibration of the C ═ O group and bending vibration of the O — H group of the carboxyl group in the carboxyl group-terminated HBM. The characteristic peaks of the two parts disappear in the infrared spectrum of the amino-terminated HBM, so that the successful synthesis of the amino-terminated hyperbranched polyamide polymer is further shown. Since the hydrogen atom signal and the characteristic peak of the terminated amino group of the sulfonated hyperbranched macromolecular polymer are not obvious, the polymer synthesized by the method is proved to be the amino-terminated HBM by a back-up method in both FIG. 3 and FIG. 4.
FIG. 5 is a FTIR spectrum of a modified PBI membrane prepared in examples 1-3, respectively, as compared to an unmodified PBI membrane obtained by solution casting from PBI powder. The infrared spectrum curve of the modified PBI film is 1200cm -1 And 1078cm -1 There are two new absorption peaks, which are derived from the symmetric and asymmetric oscillations of the sulfonic acid group in the HBM. Fig. 6 is an XRD pattern of the modified PBI membrane and the unmodified PBI membrane, from which it can be seen that PBI and its modified membrane have a broad peak at 24 ° 2 θ, indicating the presence of amorphous and crystalline scattering, while the modified PBI membrane has a reduced peak intensity with the addition of HBM, indicating that the amorphous region in the modified PBI membrane increases with the decrease of crystallinity, and the increase of amorphous region is beneficial to improve the conductivity of the proton exchange membrane. From fig. 5 and 6 we can see that HBM blended with PBI did not destroy the original structure of PBI.
Fig. 7 is an SEM image of the modified PBI membrane prepared in examples 1-3 and an unmodified PBI membrane, and it can be seen from the plan view that HBM is mixed with PBI very uniformly, and from the cross-sectional SEM image that the dense structure of PBI is not destroyed by the addition of HBM.
Fig. 8 is an AFM phase diagram of three different HBM content modified PBIs, with comparable roughness, but as the mass fraction of HBM in PBI increases from 5% to 7.5%, the HBM molecules become more prone to agglomeration, causing the phase separation of the modified PBI film to become non-uniform, possibly due to stronger hydrogen bonding effects between the HBM molecules. When the content of HBM is less, the distribution of HBM molecules in the PBI membrane is more uniform; when the content of HBM increases to a certain extent, agglomeration easily occurs between HBM molecules.
FIG. 9 is a thermogravimetric plot of modified and unmodified PBI membranes with a temperature ramp rate of 5 deg.C/min. By thermogravimetric testing, we see that both the PBI membrane and the modified PBI membrane exhibit good thermal stability, each with three weight loss steps. PBI and composite membranes begin to lose weight at 100 ℃, due to residual water and solvent in the membrane. The modified PBI membrane began a second phase weight loss at 350-450 deg.c due to sulfonate degradation in the polymer. As the temperature increases, the PBI membrane further loses weight by beginning to break at about 550 ℃ in the backbone of the membrane. The modified PBI membrane shows better thermal stability than the unmodified PBI membrane at the temperature of between 150 and 250 ℃, and the proton exchange membrane also has better electrochemical performance at high temperature.
FIG. 10 is the volume swell ratio of the modified PBI membrane soaked with unmodified PBI membrane in Phosphoric Acid (PA) at 100 ℃ for 12h and the phosphoric acid doping ratio in PA at 100 ℃ for 72 h. The volume swell ratio was calculated in the manner of (V) 2 -V 1) /V 1 The PA doping rate is calculated in the following manner 2 -M 1 )/M 1 In which V is 1 And V 2 The volume of the membrane, 1X 3cm each, before and after 12h of immersion in Phosphoric Acid (PA) at 100 ℃. M 1 And M 2 Mass of the film, 1X 3cm respectively, before and after PA doping at 100 ℃ for 72 h. From a comparison of the two sets of data, the modified PBI membrane had lower volume swell ratios at HBM mass fractions of 2.5% and 5%, which were reduced by 50% and 46.2%, respectively, compared to the unmodified PBI membrane. The phosphoric acid doping rate of the modified PBI membrane is also improved compared with that of the unmodified PBI membrane. This shows that the method of modifying PBI membrane by blending appropriate amount of HBM enhances the anti-swelling ability of PBI membrane, and due to the large amount of-NH in HBM 3 The groups enable the composite membrane to adsorb more phosphoric acid molecules.
The proton conductivity of the modified PBI membrane prepared in examples 1 to 3 and the unmodified PBI membrane is tested, as shown in fig. 11, when the doping amount of HBM is not more than 5%, the conductivity of the composite membrane is increased with the increase of the HBM content in the modified PBI membrane, when the HBM content reaches 5%, the maximum conductivity of the composite membrane reaches 170mS/cm at 180 ℃, and compared with the unmodified PBI membrane, the proton conductivity of the modified PBI at 180 ℃ is increased by about 48%.
In fig. 11, it can be seen that the proton conductivity of the modified PBI membrane increases and then decreases with the increase of the HBM content, and when the HBM content increases from 5% to 7.5%, the conductivity has been significantly decreased, and other characteristics such as AFM also indicate the reason of the decrease of the conductivity, so that the HBM content of the present invention does not increase any more after increasing to 7.5%.
As shown in fig. 12, when the proton conductivity test was performed on the modified PBI membrane and the unmodified PBI membrane under the continuous operation condition of 180 ℃, the conductivity of the modified PBI membrane with HBM content of 5% decreased by 26% after the high temperature of 180 ℃ for 100h, while the conductivity of the PBI membrane decreased by 32% after 55 h. The modified PBI membranes of examples 1-3 all had some effect in mitigating PA bleed compared to unmodified PBI membranes due to the blocking-NH of HBM 2 Can better anchor PA molecules, and the PA molecules are not easy to lose due to the hydrogen bond effect in HBM molecules and among molecules and the hyperbranched structure of HBM.
The PBI membrane is optimized in performance in multiple aspects based on the method for modifying the PBI proton exchange membrane by blending the sulfonated hyperbranched macromolecules, and a proper amount of HBM is added into the PBI membrane by the blending modification method, so that the thermal stability, the anti-swelling capacity, the proton conductivity and the like of the PBI membrane are improved, and the condition that the PA of the PBI membrane is lost at high temperature is relieved. The method is simple, has obvious effect and has good application prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for modifying a PBI proton exchange membrane based on HBM blending is characterized by comprising the following steps: the method comprises the following steps:
s1: mixing p-diaminobenzene sulfonic acid DSA and trimesic acid TA in a certain proportion, adding a certain amount of pyridine, N-methyl pyrrolidone, triphenyl phosphite and anhydrous LiCl, and carrying out polymerization reaction on the obtained mixed solution under the condition of inert atmosphere; after the reaction is finished, washing and suction filtering are carried out, and then the brown yellow sulfonated hyperbranched macromolecule HBM is obtained after NaOH solution treatment and vacuum drying;
s2: and (4) blending the HBM prepared in the step (S1) and the polybenzimidazole PBI in an organic solvent, and obtaining the modified PBI proton exchange membrane by a solution casting method, namely the HBM blending-based modified PBI proton exchange membrane.
2. The method of claim 1, wherein: the predetermined ratio in step S1 means that the molar ratio of DSA to TA is 2 or more and less than 3.
3. The method of claim 1, wherein: in step S1, the total mass of DSA and TA is 1-1.5 g.
4. The method of claim 1, wherein: the quantitative amounts stated in step S1 were 3ml of pyridine, 4ml of N-methylpyrrolidone, 1ml of triphenyl phosphite, and 0.4g of anhydrous LiCl.
5. The method of claim 1, wherein: the polymerization reaction in step S1, under the following reaction conditions: the reaction temperature is 100 ℃, and the reaction time is 0.5-2 h.
6. The method of claim 1, wherein: the blending in step S2 is carried out under the condition of 100 ℃ and fully stirred for 48 h.
7. The method of claim 1, wherein: when the HBM is blended with the PBI, the mass fraction of the HBM in the total mass of the HBM and the PBI is 2.5-7.5%.
8. The PBI proton exchange membrane prepared by the method of any one of claims 1 to 7 and based on HBM blending modification.
9. The HBM blending modification-based PBI proton exchange membrane prepared by the method of any one of claims 1 to 7 or the HBM blending modification-based PBI proton exchange membrane of claim 8 is applied to a fuel cell.
10. A fuel cell, characterized by: the proton exchange membrane comprises the HBM blending modified PBI proton exchange membrane prepared by the method of any one of claims 1 to 7 or the HBM blending modified PBI proton exchange membrane of claim 8.
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